Bendable glass stack assemblies, articles and methods of making the same

ABSTRACT

A glass element having a thickness from 25 μm to 125 μm, a first primary surface, a second primary surface, and a compressive stress region extending from the first primary surface to a first depth, the region defined by a compressive stress σI of at least about 100 MPa at the first primary surface. Further, the glass element has a stress profile such that it does not fail when it is subject to 200,000 cycles of bending to a target bend radius of from 1 mm to 20 mm, by the parallel plate method. Still further, the glass element has a puncture resistance of greater than about 1.5 kgf when the first primary surface of the glass element is loaded with a tungsten carbide ball having a diameter of 1.5 mm.

RELATED APPLICATIONS

This application is a divisional of and claims the benefit of priorityto U.S. patent application Ser. No. 15/843,346, filed on Dec. 15, 2017,which in turn, claims the benefit of priority of U.S. patent applicationSer. No. 15/398,372, filed on Jan. 4, 2017, now U.S. Pat. No. 9,898,046,issued on Feb. 20, 2018, which in turn, claims the benefit of priorityof U.S. patent application Ser. No. 15/072,027, filed on Mar. 16, 2016,now U.S. Pat. No. 9,557,773, issued on Jan. 31, 2017, which in turn,claims the benefit of priority of U.S. Pat. No. 9,321,678, issued onApr. 26, 2016, which in turn, claims the benefit of priority of U.S.Provisional Patent Application Ser. Nos. 61/932,924, 61/974,732, and62/090,604, filed on Jan. 29, 2014, Apr. 3, 2014, and Dec. 11, 2014,respectively, the contents of each of which are relied upon andincorporated herein by reference in their entireties.

TECHNICAL FIELD

The disclosure generally relates to glass stack assemblies, elements andlayers and various methods for making them. More particularly, thedisclosure relates to bendable and puncture-resistant versions of thesecomponents and methods for making them.

BACKGROUND

Flexible versions of products and components that are traditionallyrigid in nature are being conceptualized for new applications. Forexample, flexible electronic devices can provide thin, lightweight andflexible properties that offer opportunities for new applications, forexample curved displays and wearable devices. Many of these flexibleelectronic devices require flexible substrates for holding and mountingthe electronic components of these devices. Metal foils have someadvantages including thermal stability and chemical resistance, butsuffer from high cost and a lack of optical transparency. Polymericfoils have some advantages including resistance to fatigue failure, butsuffer from marginal optical transparency, lack of thermal stability andlimited hermeticity.

Some of these electronic devices also can make use of flexible displays.Optical transparency and thermal stability are often importantproperties for flexible display applications. In addition, flexibledisplays should have high fatigue and puncture resistance, includingresistance to failure at small bend radii, particularly for flexibledisplays that have touch screen functionality and/or can be folded.

Conventional flexible glass materials offer many of the neededproperties for flexible substrate and/or display applications. However,efforts to harness glass materials for these applications have beenlargely unsuccessful to date. Generally, glass substrates can bemanufactured to very low thickness levels (<25 μm) to achieve smallerand smaller bend radii. These “thin” glass substrates suffer fromlimited puncture resistance. At the same time, thicker glass substrates(>150 μm) can be fabricated with better puncture resistance, but thesesubstrates lack suitable fatigue resistance and mechanical reliabilityupon bending. Thus, there is a need for glass materials, components andassemblies for reliable use in flexible substrate and/or displayapplications and functions, particularly for flexible electronic deviceapplications.

SUMMARY

According to one aspect, a stack assembly is provided that comprises: aglass element having a thickness from about 25 μm to about 125 μm, afirst primary surface, and a second primary surface, the glass elementfurther comprising: (a) a first glass layer having a first primarysurface; and (b) a compressive stress region extending from the firstprimary surface of the glass layer to a first depth in the glass layer,the region defined by a compressive stress of at least about 100 MPa atthe first primary surface of the layer. The glass element ischaracterized by: (a) an absence of failure when the element is held ata bend radius from about 3 mm to about 20 mm for at least 60 minutes atabout 25° C. and about 50% relative humidity; (b) a puncture resistanceof greater than about 1.5 kgf when the second primary surface of theelement is supported by (i) an approximately 25 μm thickpressure-sensitive adhesive having an elastic modulus of less than about1 GPa and (ii) an approximately 50 μm thick polyethylene terephthalatelayer having an elastic modulus of less than about 10 GPa, and the firstprimary surface of the element is loaded with a stainless steel pinhaving a flat bottom with a 200 μm diameter; and (c) a pencil hardnessof greater than or equal to 8H.

According to one implementation, a foldable electronic device isprovided that includes an electronic device having a foldable feature.The foldable feature includes a stack assembly according to the firstaspect. In certain aspects, the foldable feature can include a display,printed circuit board, housing and other features of the electronicdevice.

In some embodiments, the glass element can further comprise one or moreadditional glass layers and one or more respective compressive stressregions disposed beneath the first glass layer. For example, the glasselement can comprise two, three, four or more additional glass layerswith corresponding additional compressive stress regions beneath thefirst glass layer.

According to an additional aspect, a glass article is provided thatcomprises: a glass layer having a thickness from about 25 μm to about125 μm, the layer further comprising: (a) a first primary surface; (b) asecond primary surface; and (c) a compressive stress region extendingfrom the first primary surface of the glass layer to a first depth inthe glass layer, the region defined by a compressive stress of at leastabout 100 MPa at the first primary surface of the layer. The glass layeris characterized by: (a) an absence of failure when the layer is held ata bend radius from about 3 mm to about 20 mm for at least 60 minutes atabout 25° C. and about 50% relative humidity; (b) a puncture resistanceof greater than about 1.5 kgf when the second primary surface of thelayer is supported by (i) an approximately 25 μm thickpressure-sensitive adhesive having an elastic modulus of less than about1 GPa and (ii) an approximately 50 μm thick polyethylene terephthalatelayer having an elastic modulus of less than about 10 GPa, and the firstprimary surface of the layer is loaded with a stainless steel pin havinga flat bottom with a 200 μm diameter; and (c) a pencil hardness ofgreater than or equal to 8H.

In certain aspects, the glass article may further include a glassstructure having a thickness greater than the thickness of the glasslayer and two substantially parallel edge surfaces, the structurecomprising the glass layer, wherein the layer is arranged in a centralregion of the structure between the substantially parallel edgesurfaces.

In some embodiments, the glass layer comprises an alkali-free oralkali-containing aluminosilicate, borosilicate, boroaluminosilicate, orsilicate glass composition. The thickness of the glass layer can alsorange from about 50 μm to about 100 μm. The thickness can range from 60μm to about 80 μm, according to some aspects.

In some embodiments, the bend radius of the glass element or the glasslayer can be from about 3 mm to about 20 mm. In other aspects, the bendradius can be from about 3 mm to about 10 mm. The bend radius of theglass layer can be from about 1 mm to about 5 mm in some embodiments.Further, the bend radius can also be from about 5 mm to about 7 mm.

According to certain aspects, the stack assembly can further comprise asecond layer having a low coefficient of friction disposed on the firstprimary surface of the glass element or layer. According to certainaspects, the second layer can be a coating comprising a fluorocarbonmaterial selected from the group consisting of thermoplastics andamorphous fluorocarbons. The second layer can also be a coatingcomprising one or more of the group consisting of a silicone, a wax, apolyethylene, a hot-end, a parylene, and a diamond-like coatingpreparation. Further, the second layer can be a coating comprising amaterial selected from the group consisting of zinc oxide, molybdenumdisulfide, tungsten disulfide, hexagonal boron nitride, and aluminummagnesium boride. According to some embodiments, the second layer can bea coating comprising an additive selected from the group consisting ofzinc oxide, molybdenum disulfide, tungsten disulfide, hexagonal boronnitride, and aluminum magnesium boride.

In some aspects, the compressive stress in the compressive stress regionat the first primary surface is from about 600 MPa to 1000 MPa. Thecompressive stress region can also include a maximum flaw size of 5 μmor less at the first primary surface of the glass layer. In certaincases, the compressive stress region comprises a maximum flaw size of2.5 μm or less, or even as low as 0.4 μm or less.

In other aspects, the compressive stress region comprises a plurality ofion-exchangeable metal ions and a plurality of ion-exchanged metal ions,the ion-exchanged metal ions selected so as to produce compressivestress. In some aspects, the ion-exchanged metal ions have an atomicradius larger than the atomic radius of the ion-exchangeable metal ions.According to another aspect, the glass layer can further comprise a coreregion, and a first and a second clad region disposed on the coreregion, and further wherein the coefficient of thermal expansion for thecore region is greater than the coefficient of thermal expansion for theclad regions.

According to an additional aspect, a glass article is provided thatcomprises: a glass layer having a thickness, a first primary surface,and a second primary surface. The glass layer is characterized by: (a)an absence of failure when the layer is held at a bend radius from about1 mm to about 5 mm for at least 60 minutes at about 25° C. and about 50%relative humidity; (b) a puncture resistance of greater than about 1.5kgf when the second primary surface of the layer is supported by (i) anapproximately 25 μm thick pressure-sensitive adhesive having an elasticmodulus of less than about 1 GPa and (ii) an approximately 50 μm thickpolyethylene terephthalate layer having an elastic modulus of less thanabout 10 GPa, and the first primary surface of the layer is loaded witha stainless steel pin having a flat bottom with a 200 μm diameter; and(c) a pencil hardness of greater than or equal to 8H. The glass articlealso includes a glass structure having a thickness greater than thethickness of the glass layer and two substantially parallel edgesurfaces. The structure includes the glass layer, and the layer isarranged in a central region of the structure between the substantiallyparallel edge surfaces. In some aspects, the thickness of the glassstructure may be equal to or greater than 125 μm. In an additionalaspect, the thickness of the glass layer may be set from about 20 μm toabout 125 μm to achieve the bend radius. According to an exemplaryembodiment, the thickness of the glass layer can be set from about 20 μmto about 30 μm to achieve the bend radius.

According to a further aspect, a method of making a stack assembly isprovided that comprises the steps: forming a first glass layer having afirst primary surface, a compressive stress region extending from thefirst primary surface of the glass layer to a first depth in the glasslayer, and a final thickness, wherein the region is defined by acompressive stress of at least about 100 MPa at the first primarysurface of the layer; and forming a glass element having a thicknessfrom about 25 μm to about 125 μm, the element further comprising theglass layer, a first primary surface, and a second primary surface. Theglass element is characterized by: (a) an absence of failure when theelement is held at a bend radius from about 3 mm to about 20 mm for atleast 60 minutes at about 25° C. and about 50% relative humidity; (b) apuncture resistance of greater than about 1.5 kgf when the secondprimary surface of the element is supported by (i) an approximately 25μm thick pressure-sensitive adhesive having an elastic modulus of lessthan about 1 GPa and (ii) an approximately 50 μm thick polyethyleneterephthalate layer having an elastic modulus of less than about 10 GPa,and the first primary surface of the element is loaded with a stainlesssteel pin having a flat bottom with a 200 μm diameter; and (c) a pencilhardness of greater than or equal to 8H.

In some embodiments, the step of forming the first glass layer cancomprise a forming process selected from the group consisting of fusion,slot drawing, rolling, redrawing and float processes, the formingprocess further configured to form the glass layer to the finalthickness. Other forming processes can be employed depending on thefinal shape factor for the glass layer and/or intermediate dimensions ofa glass precursor used for the final glass layer. The forming processcan also include a material removal process configured to removematerial from the glass layer to reach the final thickness.

According to some aspects of the method, the step of forming acompressive stress region extending from the first primary surface ofthe glass layer to a first depth in the glass layer comprises: providinga strengthening bath comprising a plurality of ion-exchanging metal ionshaving an atomic radius larger in size than the atomic radius of aplurality ion-exchangeable metal ions contained in the glass layer; andsubmersing the glass layer in the strengthening bath to exchange aportion of the plurality of ion-exchangeable metal ions in the glasslayer with a portion of the plurality of the ion-exchanging metal ionsin the strengthening bath to form a compressive stress region extendingfrom the first primary surface to the first depth in the glass layer. Incertain cases, the submersing step comprises submersing the glass layerin the strengthening bath at about 400° C. to about 450° C. for about 15minutes to about 180 minutes.

In certain embodiments, the method can also include a step of removingabout 1 μm to about 5 μm from the final thickness of the glass layer atthe first primary surface after the compressive stress region iscreated. The removing step can be conducted such that the compressivestress region comprises a maximum flaw size of 5 μm or less at the firstprimary surface of the glass layer. The removing step can also beconducted such that the compressive stress region comprises a maximumflaw size of 2.5 μm or less, or even as low as 0.4 μm or less, at thefirst primary surface of the glass layer.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing theembodiments as described herein, including the detailed descriptionwhich follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary, and areintended to provide an overview or framework to understanding the natureand character of the claims. The accompanying drawings are included toprovide a further understanding, and are incorporated in and constitutea part of this specification. The drawings illustrate one or moreembodiments, and together with the description serve to explainprinciples and operation of the various embodiments. Directional termsas used herein—for example, up, down, right, left, front, back, top,bottom—are made only with reference to the figures as drawn and are notintended to imply absolute orientation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a stack assembly comprising a glasselement with a glass layer according to an aspect of this disclosure.

FIG. 1A is perspective view of the stack assembly depicted in FIG. 1subjected to bending forces.

FIG. 1B is a cross-sectional view of the stack assembly depicted in FIG.1.

FIG. 1C is a cross-sectional view of a stack assembly comprising a glasselement with compressive stress regions formed by an ion exchangeprocess according to a further aspect of this disclosure.

FIG. 1D is a cross-sectional view of a stack assembly comprising a glasselement having a glass layer with a core region and two clad regionsaccording to an aspect of this disclosure.

FIG. 2 is a perspective view of a stack assembly comprising a glasselement with three glass layers according a further aspect of thisdisclosure.

FIG. 2A is a perspective view of the stack assembly depicted in FIG. 2subjected to bending forces.

FIG. 3 is a perspective view of a stack assembly comprising a glassstructure and a glass element according to an aspect of this disclosure.

FIG. 3A is a perspective view of the stack assembly depicted in FIG. 3subjected to bending forces.

FIG. 3B is a cross-sectional view of the stack assembly depicted in FIG.3.

FIG. 4 is a perspective view of a stack assembly comprising a glassstructure and a glass element according to an aspect of this disclosure.

FIG. 4A is a perspective view of the stack assembly depicted in FIG. 4subjected to bending forces.

FIG. 4B is a cross-sectional view of the stack assembly depicted in FIG.4.

FIG. 5 is a plot of failure puncture load test data as a function ofthickness of a glass layer according to an aspect of this disclosure.

FIG. 6A is a plot of compressive stress vs. depth in a 75 μm thick glasssample after an ion exchange process step according to an aspect of thisdisclosure.

FIG. 6B is a plot of compressive stress vs. depth in a 75 μm thick glasssample after an ion exchange process step and a light etching stepaccording to an aspect of this disclosure.

FIG. 7A is a schematic plot of estimated stress intensity factors forglass layers of three compositions having a thickness of 25, 50 and 100μm and a bend radius of 3, 5 and 7 mm.

FIG. 7B is a schematic plot of estimated stress intensity factors forglass layers of three compositions having a thickness of 50 μm and abend radius of 5 mm, with and without a compressive stress region,according to an aspect of this disclosure.

FIG. 8 is a schematic plot of estimated maximum stress levels at thesurface of glass layers of one composition having thickness of 25, 50,75 and 100 μm and a bend radius of 5 mm, with and without a compressivestress region developed through an ion exchange process, according to afurther aspect of this disclosure.

FIG. 9 is a plot of failure puncture load test data for glass layers ofone composition having a thickness of 75 μm and a compressive stressregion developed through an ion exchange process, according to an aspectof this disclosure.

FIG. 10 is a schematic plot of estimated stress intensity factors forglass layers of three compositions having a thickness of 25, 50, 75 and100 μm, a bend radius of 10 and 20 mm, and a compressive stress regiondeveloped through a mismatch in the coefficient of thermal expansionbetween core and cladding regions of the glass layers, according to afurther aspect of this disclosure.

FIG. 11 is a Weibull plot of failure probability vs. load at failure fortwo groups of glass samples according to an aspect of this disclosure.

FIG. 12 is a stress profile for a glass element according to aspects ofthe disclosure when compressive stress results from metal ion exchangebetween salt and glass.

FIG. 13 is a stress profile for a glass element according to aspects ofthe disclosure when subject to a bending stress.

FIG. 14 is a resultant stress profile showing the stress profiles ofFIG. 12 and FIG. 13 added together.

FIG. 15 is a Weibull plot of failure probability vs. strength under twopoint bending of various different glass samples.

FIG. 16 is a Weibull plot of failure probability vs. strength under twopoint bending of various different glass samples after cube cornercontact.

FIG. 17 is a sample glass according to aspects of the disclosure afterindentation with Vickers indenter under 1 kgf load.

FIG. 18 is a sample glass according to aspects of the disclosure afterindentation with a Vickers indenter under 2 kgf load.

FIG. 19 is a comparative glass after indentation with Vickers indenterunder 1 kgf load.

FIG. 20 is a comparative glass after indentation with a Vickers indenterunder 2 kgf load.

FIG. 21 is a two point bend test configuration.

DETAILED DESCRIPTION

Reference will now be made in detail to the present preferredembodiments, examples of which are illustrated in the accompanyingdrawings. Whenever possible, the same reference numerals will be usedthroughout the drawings to refer to the same or like parts. Ranges canbe expressed herein as from “about” one particular value, and/or to“about” another particular value. When such a range is expressed,another embodiment includes from the one particular value and/or to theother particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another embodiment. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint.

Among other features and benefits, the stack assemblies, glass elementsand glass articles (and the methods of making them) of the presentdisclosure provide mechanical reliability (e.g., in static tension andfatigue) at small bend radii as well as high puncture resistance. Thesmall bend radii and puncture resistance are beneficial when the stackassembly, glass element, and/or glass article, are used in a foldabledisplay, for example, one wherein one part of the display is folded overon top of another portion of the display. For example, the stackassembly, glass element and/or glass article, may be used as one or moreof: a cover on the user-facing portion of a foldable display, a locationwherein puncture resistance is particularly important; a substrate,disposed internally within the device itself, on which electroniccomponents are disposed; or elsewhere in a foldable display device.Alternatively, the stack assembly, glass element, and or glass article,may be used in a device not having a display, but one wherein a glasslayer is used for its beneficial properties and is folded, in a similarmanner as in a foldable display, to a tight bend radius. The punctureresistance is particularly beneficial when the stack assembly, glasselement, and/or glass article, are used on the exterior of the device,wherein a user will interact with it.

Referring to FIGS. 1 and 1B, a stack assembly 100 is depicted thatincludes a glass element 50. Glass element 50 has a glass elementthickness 52, a first primary surface 54 and a second primary surface56. Thickness 52 can range from about 25 μm to about 125 μm in someaspects. In other aspects, thickness 52 can range from about 50 μm toabout 100 μm, or about 60 μm to about 80 μm. Thickness 52 can also beset at other thicknesses between the foregoing ranges.

The glass element 50 includes a glass layer 50 a with a glass layerfirst primary surface 54 a and a glass layer second primary surface 56a. In addition, glass layer 50 a also includes edges 58 b, generallyconfigured at right angles to the primary surfaces 54 a and 56 a. Glasslayer 50 a is further defined by a glass layer thickness 52 a. In theaspect of stack assembly 100 depicted in FIGS. 1 and 1B, the glasselement 50 includes one glass layer 50 a. As a consequence, the glasslayer thickness 52 a is comparable to the glass element thickness 52 forstack assembly 100. In other aspects, glass element 50 can include twoor more glass layers 50 a (see, e.g., stack assembly 100 c in FIG. 2 andthe corresponding description). As such, the thickness 52 a of glasslayer 50 a can range from about 1 μm to about 125 μm. For example, glasselement 50 can include three glass layers 50 a, each having a thickness52 a of about 8 μm. In this example, the thickness 52 of glass element50 may be about 24 μm. It should also be understood, however, that glasselement 50 could include other non-glass layers (e.g., compliant polymerlayers) in addition to one or more glass layers 50 a.

In FIGS. 1 and 1B, glass layer 50 a can be fabricated from alkali-freealuminosilicate, borosilicate, boroaluminosilicate, and silicate glasscompositions. Glass layer 50 a can also be fabricated fromalkali-containing aluminosilicate, borosilicate, boroaluminosilicate,and silicate glass compositions. In certain aspects, alkaline earthmodifiers can be added to any of the foregoing compositions for glasslayer 50 a. In one exemplary aspect, glass compositions according to thefollowing are suitable for the glass layer 50 a: SiO₂ at 64 to 69% (bymol %); Al₂O₃ at 5 to 12%; B₂O₃ at 8 to 23%; MgO at 0.5 to 2.5%; CaO at1 to 9%; SrO at 0 to 5%; BaO at 0 to 5%; SnO₂ at 0.1 to 0.4%; ZrO₂ at 0to 0.1%; and Na₂O at 0 to 1%. In another exemplary aspect, the followingcomposition is suitable for the glass layer 50 a: SiO₂ at ˜67.4% (by mol%); Al₂O₃ at ˜12.7%; B₂O₃ at ˜3.7%; MgO at ˜2.4%; CaO at 0%; SrO at 0%;SnO₂ at ˜0.1%; and Na₂O at ˜13.7%. In a further exemplary aspect, thefollowing composition is also suitable for the glass layer 50 a: SiO₂ at68.9% (by mol %); Al₂O₃ at 10.3%; Na₂O at 15.2%; MgO at 5.4%; and SnO₂at 0.2%. In some aspects, a composition for glass layer 50 a is selectedwith a relatively low elastic modulus (compared to other alternativeglasses). Lower elastic modulus in the glass layer 50 a can reduce thetensile stress in the layer 50 a during bending. Other criteria can beused to select the composition for glass layer 50 a, including but notlimited to ease of manufacturing to low thickness levels whileminimizing the incorporation of flaws, ease of development of acompressive stress region to offset tensile stresses generated duringbending, optical transparency, and corrosion resistance.

The glass element 50 and the glass layer 50 a can adopt a variety ofphysical forms. From a cross-sectional perspective, the element 50 andthe layer 50 a (or layers 50 a) can be flat or planar. In some aspects,element 50 and layer 50 a can be fabricated in non-rectilinear,sheet-like forms depending on the final application. As an example, amobile display device having an elliptical display and bezel couldrequire a glass element 50 and layer 50 a having a generally elliptical,sheet-like form.

Still referring to FIGS. 1 and 1B, the glass element 50 of the stackassembly 100 further includes a compressive stress region 60 thatextends from the first primary surface 54 a of the glass layer 50 to afirst depth 62 in the glass layer 50. Among other advantages, thecompressive stress region 60 can be employed within the glass layer 50 ato offset tensile stresses generated in the glass layer 50 a uponbending, particularly tensile stresses that reach a maximum near thefirst primary surface 54 a. The compressive stress region 60 can includea compressive stress of at least about 100 MPa at the first primarysurface of the layer 54 a. In some aspects, the compressive stress atthe first primary surface 54 a is from about 600 MPa to about 1000 MPa.In other aspects, the compressive stress can exceed 1000 MPa at thefirst primary surface 54 a, up to 2000 MPa, depending on the processemployed to produce the compressive stress in the glass layer 50 a. Thecompressive stress can also range from about 100 MPa to about 600 MPa atthe first primary surface 54 a in other aspects of this disclosure.

Within the compressive stress region 60, the compressive stress can stayconstant, decrease or increase within the glass layer 50 a as a functionof depth from the first primary surface of the glass layer 54 a down tothe first depth 62. As such, various compressive stress profiles can beemployed in compressive stress region 60. Further, the depth 62 can beset at approximately 15 μm or less from the first primary surface of theglass layer 54 a. In other aspects, the depth 62 can be set such that itis approximately ⅓ of the thickness 52 a of the glass layer 50 a orless, or 20% of the thickness 52 a of the glass layer 50 a or less, fromthe first primary surface of the glass layer 54 a.

Referring to FIGS. 1 and 1A, the glass element 50 is characterized by anabsence of failure when the element is held at the bend radius 40 fromabout 3 mm to about 20 mm for at least 60 minutes at about 25° C. andabout 50% relative humidity. As used herein, the terms “fail,” “failure”and the like refer to breakage, destruction, delamination, crackpropagation or other mechanisms that leave the stack assemblies, glassarticles, and glass elements of this disclosure unsuitable for theirintended purpose. When the glass element 50 is held at the bend radius40 under these conditions, bending forces 42 are applied to the ends ofthe element 50. In general, tensile stresses are generated at the firstprimary surface 54 of the element 50 and compressive stresses aregenerated at the second primary surface 56 during the application ofbending forces 42. In other aspects, glass element 50 can be configuredto avoid failure for bend radii that range from about 3 mm to about 10mm. In some aspects, the bend radius 40 can be set in a range from about1 mm to about 5 mm. The bend radius 40 can also be set to a range fromabout 5 mm to 7 mm without causing a failure in the glass element 50according to other aspects of stack assembly 100. The glass element 50can be also characterized in some aspects by an absence of failure whenthe element is held at a bend radius 40 from about 3 mm to about 20 mmfor at least 120 hours at about 25° C. and about 50% relative humidity.Bend testing results can vary under testing conditions with temperaturesand/or humidity levels that differ from the foregoing. For example, aglass element 50 having a smaller bend radii 40 (e.g., <3 mm) may becharacterized by an absence of failure in bend testing conducted athumidity levels significantly below 50% relative humidity.

The glass element 50 is also characterized by a puncture resistance ofgreater than about 1.5 kgf when the second primary surface 56 of theelement 50 is supported by (i) an approximately 25 μm thickpressure-sensitive adhesive (“PSA”) having an elastic modulus of lessthan about 1 GPa and (ii) an approximately 50 μm thick polyethyleneterephthalate layer (“PET”) having an elastic modulus of less than about10 GPa, and the first primary surface 54 of the element 50 is loadedwith a stainless steel pin having a flat bottom with a 200 μm diameter.Typically, puncture testing according to aspects of this disclosure isperformed under displacement control at 0.5 mm/min cross-head speed. Incertain aspects, the stainless steel pin is replaced with a new pinafter a specified quantity of tests (e.g., 10 tests) to avoid bias thatcould result from deformation of the metal pin associated with thetesting of materials possessing a higher elastic modulus (e.g., glasselement 50). In some aspects, the glass element 50 is characterized by apuncture resistance of greater than about 1.5 kgf at a 5% or greaterfailure probability within a Weibull plot. The glass element 50 can alsobe characterized by a puncture resistance of greater than about 3 kgf atthe Weibull characteristic strength (i.e., a 63.2% or greater). Incertain aspects, the glass element 50 of the stack assembly 100 canresist puncture at about 2 kgf or greater, 2.5 kgf or greater, 3 kgf orgreater, 3.5 kgf or greater, 4 kgf or greater, and even higher ranges.The glass element 50 is also characterized by a pencil hardness ofgreater than or equal to 8H.

Referring again to FIGS. 1 and 1B, some aspects of the stack assembly100 include a second layer 70 having a low coefficient of friction witha second layer coating thickness 72. In these configurations, the secondlayer 70 is disposed on the first primary surface 54 of the glasselement 50. When employed in stack assembly 100 for certainapplications, the second layer 70 can serve to decrease friction and/orreduce surface damage from abrasion. The second layer 70 can alsoprovide a measure of safety in retaining pieces and shards of glasselement 50 and/or layer 50 a when the element and/or layer has beensubjected to stresses in excess of its design limitations that causefailure. The thickness 72 of the second layer 70 can be set at 1micrometer (μm) or less in some aspects. In other aspects, the secondlayer 70 can be set at 500 nm or less, or as low as 10 nm or less forcertain compositions. Further, in some aspects of stack assembly 100, anadditional layer 70 can be employed on the primary surface 56 to providea safety benefit in retaining shards of glass element 50 and/or layer 50a that have resulted from stresses in excess of their designrequirements.

Second layer 70 can employ various fluorocarbon materials that are knownto have low surface energy, including thermoplastics for example,polytetrafluoroethylene (“PTFE”), fluorinated ethylene propylene(“FEP”), polyvinylidene fluoride (“PVDF”), and amorphous fluorocarbons(e.g., DuPont® Teflon® AF and Asahi® Cytop® coatings) which typicallyrely on mechanical interlocking mechanisms for adhesion. Second layer 70can also be fabricated from silane-containing preparation for example,Dow Corning® 2634 coating or other fluoro- or perfluorosilanes (e.g.,alkylsilanes) which can be deposited as a monolayer or a multilayer. Insome aspects, second layer 70 can include silicone resins, waxes,polyethylene (oxided) used by themselves or in conjunction with ahot-end coating for example, tin oxide, or vapor-deposited coatings forexample, parylene and diamond-like coatings (“DLCs”). Second layer 70can also include zinc oxide, molybdenum disulfide, tungsten disulfide,hexagonal boron nitride, or aluminum magnesium boride that can be usedeither alone or as an additive in the foregoing coating compositions andpreparations.

Alternatively or in addition to the above, the second layer 70 mayinclude various other attributes, such as anti-microbial, anti-splinter,anti-smudge, and anti-fingerprint.

In some aspects, the stack assembly 100 can include a glass element 50having a compressive stress region 60 with a maximum flaw size of 5 μmor less at the first primary surface 54 a of the glass layer 50. Themaximum flaw size can also be held to 2.5 μm or less, 2 μm or less, 1.5μm or less, 0.5 μm or less, 0.4 μm or less, or even smaller flaw sizeranges. Reducing the flaw size in the compressive stress region of theglass element 50, the layer 50 a and/or the layers 50 a can furtherreduce the propensity of these elements and/or layers to fail by crackpropagation upon the application of tensile stresses by virtue ofbending forces, for example, bending forces 42 (see FIG. 1A). Inaddition, some aspects of stack assembly 100 can include a surfaceregion with a controlled flaw size distribution (e.g., flaw sizes of 0.5μm or less at the first primary surface 54 a of the glass layer 50 a)that also lacks the superposition of a compressive stress region.

Referring again to FIG. 1A, bending forces 42 applied to the stackassembly 100 result in tensile stresses at the first primary surface 54of the glass element 50. Tighter bending radii 40 lead to higher tensilestresses. Equation (1) below can be used to estimate the maximum tensilestresses in the stack assembly 100, particularly at the first primarysurface 54 of the glass element 50, subjected to bending with a constantbend radius 40. Equation (1) is given by:

$\begin{matrix}{\sigma_{{ma}\; x} = {\frac{E}{1 - v^{2}}\frac{h}{2}\frac{1}{R}}} & (1)\end{matrix}$where E is the Young's modulus of the glass element 50, v is thePoisson's ratio of the glass element 50 (typically v is ˜0.2-0.3 formost glass compositions), h is reflective of the thickness 52 of theglass element, and R is the bend radius of curvature (comparable to bendradius 40). Using Equation (1), it is apparent that maximum bendingstresses are linearly dependent on the thickness 52 of the glass elementand elastic modulus, and inversely dependent on the bend radius 40 ofcurvature of the glass element.

The bending forces 42 applied to the stack assembly 100 could alsoresult in the potential for crack propagation leading to instantaneousor slower, fatigue failure mechanisms. The presence of flaws at thefirst primary surface 54, or just beneath the surface, of the element 50can contribute to these potential failure modes. Using Equation (2)below, it is possible to estimate the stress intensity factor in a glasselement 50 subjected to bending forces 42. Equation (2) is given by:

$\begin{matrix}{K = {{Y\;\sigma\sqrt{\pi\; a}} = {\frac{YE}{1 - v^{2}}\frac{h}{2}\frac{1}{R}\sqrt{\pi\; a}}}} & (2)\end{matrix}$where α is the flaw size, Y is a geometry factor (generally assumed tobe 1.12 for cracks emanating from a glass edge, a typical failure mode),and σ is the bending stress associated with the bending forces 42 asestimated using Equation (1). Equation (2) assumes that the stress alongthe crack face is constant, which is a reasonable assumption when theflaw size is small (e.g., <1 μm). When the stress intensity factor Kreaches the fracture toughness of the glass element 50, K_(IC),instantaneous failure will occur. For most compositions suitable for usein glass element 50, K_(IC) is ˜0.7 MPa√m. Similarly, when K reaches alevel at or above a fatigue threshold, K_(threshold), failure can alsooccur via slow, cyclic fatigue loading conditions. A reasonableassumption for K_(threshold) is ˜0.2 MPa√m. However, K_(threshold) canbe experimentally determined and is dependent upon the overallapplication requirements (e.g., a higher fatigue life for a givenapplication can increase K_(threshold)). In view of Equation (2), thestress intensity factor can be reduced by reducing the overall tensilestress level and/or the flaw size at the surface of the glass element50.

According to some aspects of stack assembly 100, the tensile stress andstress intensity factor estimated through Equations (1) and (2) can beminimized through the control of the stress distribution at the firstprimary surface 54 of the glass element 50. In particular, a compressivestress profile (e.g., a compressive stress region 60) at and below thefirst primary surface 54 is subtracted from the bending stresscalculated in Equation (1). As such, overall bending stress levels arereduced which, in turn, also reduces the stress intensity factors thatcan be estimated through Equation (2).

In some implementations, a foldable electronic device with a foldablefeature can include the stack assembly 100. The foldable feature, forexample, can be a display, printed circuit board, housing or otherfeatures associated with the electronic device. When the foldablefeature is a display, for example, the stack assembly 100 can besubstantially transparent. Further, the stack assembly 100 can havepencil hardness, bend radius and/or puncture resistance capabilities asdescribed in the foregoing. In one exemplary implementation, thefoldable electronic device is a wearable electronic device, such as awatch, wallet or bracelet, that includes or otherwise incorporates thestack assembly 100 described according to the foregoing. As definedherein, “foldable” includes complete folding, partial folding, bending,flexing, and multiple-fold capabilities.

Referring to FIG. 1C, a cross-section of a stack assembly 100 a isdepicted that relies on an ion exchange process to develop a compressivestress region 60 a. Stack assembly 100 a is similar to the stackassembly 100 depicted in FIGS. 1-1B, and like-numbered elements havecomparable structure and function. In stack assembly 100 a, however, thecompressive stress region 60 a of the glass element 50 can be developedthrough an ion exchange process. That is, the compressive stress region60 a can include a plurality of ion-exchangeable metal ions and aplurality of ion-exchanged metal ions, the ion-exchanged metal ionsselected so as to produce compressive stress in the region 60 a. In someaspects of stack assembly 100 a, the ion-exchanged metal ions have anatomic radius larger than the atomic radius of the ion-exchangeablemetal ions. The ion-exchangeable ions (e.g., Na⁺ ions) are present inthe glass element 50 and the layer 50 a before being subjected to theion exchange process. Ion-exchanging ions (e.g., K⁺ ions) can beincorporated into the glass element 50 and layer 50 a, replacing some ofthe ion-exchangeable ions. The incorporation of ion-exchanging ions, forexample, K⁺ ions, into the glass element 50 and the layer 50 a can beeffected by submersing the element or the layer in a molten salt bathcontaining ion-exchanging ions (e.g., molten KNO₃ salt). In thisexample, the K⁺ ions have a larger atomic radius than the Na³⁰ ions andtend to generate local compressive stresses in the glass whereverpresent.

Depending on the ion-exchanging process conditions employed, theion-exchanging ions can be imparted from the first primary surface 54 adown to a first ion exchange depth 62 a, establishing an ion exchangedepth-of-layer (“DOL”) for the compressive stress region 60 a.Similarly, a second compressive stress region 60 a can be developed fromthe second primary surface 56 a down to a second ion exchange depth 63 aas depicted in FIG. 1C. Compressive stress levels within the DOL thatfar exceed 100 MPa can be achieved with such ion exchange processes, upto as high as 2000 MPa. As noted earlier, the compressive stress levelsin the compressive stress region 60 a (and a second region 60 a whenpresent) can serve to offset the tensile stresses generated in the stackassembly 100 a, glass element 50 and glass layer 50 a generated frombending forces 42.

Referring again to FIG. 1C, some aspects of stack assembly 100 a caninclude one or more edge compressive stress regions 59 a, each definedby a compressive stress of at least 100 MPa. An edge compressive stressregion 59 a in the glass element 50 can be established from an edge 58 bdown to an edge depth 59 b. Ion-exchanging processes similar in natureto those employed to generate the compressive stress region 60 a can bedeployed to generate an edge compressive stress region 59 a. Morespecifically, the edge compressive stress region 59 a can be used tooffset tensile stresses generated at the edge 58 b through, for example,bending of the glass element 50 across the face of the edge 58 b.Alternatively, or as an addition thereto, without being bound by theory,the compress stress region 59 a may offset adverse effects from animpact or abrasion event at or to the edge 58 b.

In FIG. 1D, a stack assembly 100 b is depicted that relies on a mismatchin the coefficient of thermal expansion (“CTE”) between regions of theglass layer 50 a to develop compressive stress regions 60 b. Stackassembly 100 b is similar to the stack assembly 100 depicted in FIGS.1-1B, and like-numbered elements have comparable structure and function.In stack assembly 100 b, however, the compressive stress regions 60 b ofthe glass element 50 can be developed via the tailored structure ofglass layer 50 a which relies on CTE differences within the layer 50 aitself. In particular, the glass layer 50 a includes a core region 55 aand a first and a second clad region 57 a disposed on the core region 55a. Notably, the CTE of the core region 55 a is greater than the CTE ofthe clad regions 57 a. After the glass layer 50 a is cooled duringfabrication, the CTE differences between the core region 55 a and theclad regions 57 a cause uneven volumetric contraction upon cooling,leading to the development of compressive stress regions 60 b in theclad regions 57 a, below the respective first and second primarysurfaces 54 a and 56 a as shown in FIG. 1D. Put another way, the coreregion 55 a and the clad regions 57 a are brought into intimate contactwith one another at high temperatures; and regions 55 a and 57 a arethen cooled to a low temperature such that the greater volume change ofthe high CTE core region 55 a relative to the low CTE clad regions 57 acreates the compressive stress regions 60 b in the clad regions 57 a.

Referring again to FIG. 1D, the CTE-developed compressive stress regions60 b reach from the first primary surface of the glass layer 54 a downto a CTE region depth 62 b, and from the second primary surface 56 adown to a CTE region depth 63 b, thus establishing CTE-related DOLs. Insome aspects, the compressive stress levels in the compressive stressregions 60 b can exceed 150 MPa. Maximizing the difference in CTE valuesbetween the core region 55 a and the clad regions 57 a can increase themagnitude of the compressive stress developed in the compressive stressregions 60 b upon cooling of the element 50 after fabrication.

In some aspects of stack assembly 100 b, the core region 55 a has a coreregion thickness 55 b and the clad regions 57 a have a clad thickness 57b as shown in FIG. 1D. In these aspects, it is preferable to set athickness ratio of greater than or equal to 3 for the core regionthickness 55 b divided by the sum of the clad region thicknesses 57 b.As such, maximizing the size of the core region 55 a and/or its CTErelative to the size and/or CTE of the clad regions 57 a can serve toincrease the magnitude of the compressive stress levels observed in thecompressive stress regions 60 b of the stack assembly 100 b.

According to another aspect, FIG. 2 depicts a stack assembly 100 c witha glass element 50 having multiple glass layers 50 a (e.g., two layers50 a, three layers 50 a, four layers 50 a, and so on). As shown in FIG.2, the three glass layers 50 a, stacked together, make up the glasselement 50. A compressive stress region 60 can be present in each layer50 a as shown in FIG. 2. The layers 50 a can be stacked directlytogether or, in some aspects, compliant interlayers can be disposedbetween them. Further, in some aspects of stack assembly 100 c, acompressive stress region 60 is not required in all layers 50 a withinthe glass element 50. Preferably, a compressive stress region 60 ispresent in the topmost layer 50 a of the element 50. In addition, it isalso preferable in some aspects to include edge compressive stressregions 59 a (see FIG. 1C and the corresponding description),compressive stress regions 60 a (see FIG. 1C and the correspondingdescription), and/or compressive stress regions 60 b (see FIG. 1D andthe corresponding description) in one or more layers 50 a.

In general, the layers 50 a of the stack assembly 100 c are configuredto allow movement with respect to one another upon bending of the glasselement 50 (see FIG. 2A); or the layers 50 a are loosely coupled to oneanother. The collective thickness of the glass element 50 obtainedthrough the stacking of layers 50 a can increase the resistance of theelement 50 to puncture, as each layer 50 a supports the layer above it.Further, the ability of the glass layers 50 a to move relative to oneanother during bending reduces the amount of tensile stress generated ineach layer 50 a upon bending to a bend radius 40. This is because thethickness of each layer 50 a (rather than the thickness of element 50)is the contributing factor in generating the tensile stress, asestimated by Equation (1). Because each layer 50 a is generallydecoupled, in terms of generating bending stresses, from its adjacentlayer 50 a, some aspects of the stack assembly 100 c incorporate acompressive stress region 60 within each layer 50 a present in the stackassembly. In certain aspects of stack assembly 100 c, a second layer 70can be disposed on the first primary surface 54 of the glass element 50(i.e., on the first primary surface of the top-most layer 50 a). Asecond layer 70 employed for this purpose has a comparable structure andfunction to the second layer 70 outlined earlier in connection with thestack assembly 100. Alternatively, or as an addition thereto, a secondlayer 70 may be employed: on the second primary surface of thelower-most layer 50 a; and/or on one or both primary surfaces of anylayer 50 a in the stack assembly 100 c.

Referring to FIGS. 3 and 3B, a stack assembly (or glass article) 100 dis depicted according to an additional aspect of this disclosure. Stackassembly 100 d includes a glass structure 90 having a thickness 92 thatis greater than the thickness 52 a of its glass layer 50 a. Glass layer50 a includes a first primary surface 54 a and a second primary surface56 a. The first primary surface 54 a also can extend to the firstprimary surface of the glass structure 90 (see FIGS. 3 and 3B). In someaspects, the glass structure 90 has a thickness 92 that is greater thanor equal to 125 μm. According to an exemplary embodiment, the thickness52 a of the glass layer can be set from about 20 μm to about 125 μm. Incertain aspects of stack assembly 100 d, a second layer 70 can bedisposed on the first primary surface 54 a of the glass layer 50 a andglass structure 90. A second layer 70 employed for this purpose in thestack assembly 100 d has a comparable structure and function to thesecond layer 70 outlined earlier in connection with the stack assembly100.

As shown in FIGS. 3 and 3B, the glass structure 90 and the glass layer50 a of the stack assembly/glass article 100 d are monolithic withregard to one another. However, in some aspects, the glass structure 90can be a separate component that is bonded or otherwise joined to glasslayer 50 a. Further, in stack assembly 100 d, the glass layer 50 a isarranged in a central region 96 of the glass structure 90, between thesubstantially parallel edges 98 of the glass structure. In some aspects,and as depicted in FIGS. 3 and 3B, the glass layer 50 a and centralregion 96 are spaced some distance from each of the parallel edges 98.In other aspects, the glass layer 50 a and central region 96 can bespaced closer to one edge 98 than the other substantially parallel edge98.

In the stack assembly (or glass article) 100 d depicted in FIGS. 3 and3B, the glass layer 50 a, as incorporated into the glass structure 90,is essentially the same as the glass layer 50 a described in theforegoing in connection with stack assemblies 100, 100 a and 100 b. Assuch, the glass layer 50 a employed in stack assembly 100 d includes acompressive stress region 60, 60 a or 60 b that spans from the firstprimary surface 54 a of the glass layer 50 a down to the first depth 62a. According to some aspects of the stack assembly 100 d, thecompressive stress region 60, 60 a, or 60 b within the glass layer 50 acan also span laterally into the glass structure 90. While not requiredin all aspects, the inclusion of the compressive stress region 60, 60 aor 60 b throughout the glass layer 50 a and the glass structure 90 canprovide a manufacturability benefit. For example, an ion exchangeprocess could be employed to develop the compressive stress region 60 or60 a in both the glass layer 50 a and the glass structure 90 in onesubmersion step.

As shown in FIG. 3A, the stack assembly 100 d (or glass article) can besubjected to bending forces 42 that bend the glass layer 50 a upon aconstant bend radius 40. Since the thickness 52 a of the glass layer 50a is generally smaller than the thickness 92 of the glass structure 90,the bending forces 42 tend to cause bending displacements in the glasslayer 50 a and little or no bending in the adjacent sections of theglass structure 90. As such, the bending stress and stress intensitylevels are reduced at the first primary surface 54 a of the glass layer50 a by virtue of minimizing the thickness 52 a to levels below thethickness 92 of the glass structure 90. Nevertheless, the increasedthickness 92 of the glass structure 90 provides additional punctureresistance for the majority of the stack assembly 100 d (i.e., beyondthat in the central region 96 containing the glass layer 50 a).

In some additional aspects of stack assembly 100 d, the central region96 beneath the glass layer 50 a and second primary surface 56 a can befurther reinforced with a generally non-compliant, polymeric layer. Thisreinforcement can tend to offset any reduced puncture resistance in theglass layer 50 a relative to the puncture resistance of the glassstructure 90. Further, the compressive stress region 60, 60 a or 60 bemployed in the glass layer 50 a of the stack assembly 100 d can bedeveloped through the ion exchange processes and/or CTE mismatchconcepts outlined earlier in connection with stack assemblies 100 a and100 b (see FIGS. 1C and 1D and the corresponding description).

As shown in FIGS. 4, 4A and 4B, a glass article or stack assembly 100 eis provided that comprises: a glass layer 50 e having a thickness 52 e,a first primary surface 54 e, and a second primary surface 56 e. Thefirst primary surface 54 e also can extend to the first primary surfaceof the glass structure 90 (see FIGS. 4 and 4B). In some aspects, theglass structure 90 has a thickness 92 that is greater than or equal to125 μm. According to an exemplary embodiment, the thickness 52 e of theglass layer 50 e can be set from about 20 μm to about 125 μm. In certainaspects of stack assembly 100 e, a second layer 70 can be disposed onthe first primary surface 54 e of the glass layer 50 e and/or on one orboth primary surfaces of glass structure 90. A second layer 70 employedfor this purpose in the stack assembly 100 e has a comparable structureand function to the second layer 70 outlined earlier in connection withthe stack assembly 100. A second layer 70 may also be disposed on thesecond primary surface 56 e.

In the stack assembly (or glass article) 100 e depicted in FIGS. 4 and4B, the glass layer 50 e, as incorporated into the glass structure 90,is essentially the same as the glass layer 50 a described in theforegoing in connection with stack assemblies 100, 100 a and 100 b.Furthermore, the structure and arrangement of the stack assembly 100 eis similar to the stack assembly 100 d described earlier in connectionwith FIGS. 3, 3A and 3B. However, the glass layer 50 e employed in stackassembly 100 e does not include a compressive stress region 60.

As shown in FIG. 4A, the stack assembly 100 e (or glass article) can besubjected to bending forces 42 that bend the glass layer 50 e upon aconstant bend radius 40. Since the thickness 52 e of the glass layer 50e is generally smaller than the thickness 92 of the glass structure 90,the bending forces 42 tend to cause bending displacements in the glasslayer 50 e and little or no bending in the adjacent sections of theglass structure 90. As such, the bending stress and stress intensitylevels are reduced at the first primary surface 54 e of the glass layer50 e by virtue of minimizing the thickness 52 e to levels below thethickness 92 of the glass structure 90.

In stack assembly 100 e (or glass article), however, the increasedthickness 92 of the glass structure 90 provides additional punctureresistance for the majority of the assembly (i.e., beyond that in thecentral region 96 containing the glass layer 50 e). As demonstrated bythe results depicted in FIG. 5, puncture resistance and glass thicknesscan be correlated. The results in FIG. 5 were generated by measuring thepuncture resistance of various glass samples having thicknessesincluding 116, 102, 87, 71, 60, 49, 33 and 25 μm. These glass sampleswere prepared by etching 130 μm-thick glass samples to the foregoingthickness levels using an etching solution having 15 vol % HF and 15 vol% HCl. Puncture resistance testing was performed on each glass sample,as laminated to a 375 μm compliant layer stack to simulate the structureof a flexible display device. The 375 μm thick compliant layer stackconsisted of the following layers: (a) a 50 μm thick PSA layer, (b) a100 μm thick PET layer, and (c) a 100 μm thick PSA layer, and (d) a 125μm thick PET layer. Once each glass sample (e.g., 116 μm thick glass,102 μm thick glass, etc.) was laminated to the 375 μm thick compliantlayer stack, a flat tip probe having a 200 μm diameter stainless steeltip was pushed into a primary surface of the glass sample opposite fromthe compliant layer stack. The tip was then advanced into the sampleuntil failure (as verified by visual observation with an opticalmicroscope) and the force at failure was measured (in units of kgf). Theresults from this testing were plotted in FIG. 5.

As the results from FIG. 5 demonstrate, the puncture resistance of theglass samples decreased from about 2.5 kgf to about 0.4 kgf withdecreasing glass layer thickness from about 116 μm to about 25 μm,respectively. Hence, the puncture resistance of these glass samples washighly dependent on glass thickness. In addition, FIG. 5 demonstratesthat the puncture resistance for the tested glass substrate samplehaving a thickness of about 116 μm is about 2.5 kgf. It is evidentthrough extrapolation that puncture resistance levels that can exceed 3kgf can be obtained through the use of glass substrates having athickness of 130 μm or greater. As such, one aspect of stack assembly100 e (see FIGS. 4, 4A and 4B) employs a glass structure 90 having athickness of about 130 μm or greater to obtain a puncture resistance of3 kgf (in the regions of stack assembly 100 e beyond those in proximityto the central region 96 containing the thinner, glass layer 50 e). Insome additional aspects of the stack assembly 100 e, the central region96 beneath the glass layer 50 e and second primary surface 56 e can befurther reinforced with a generally non-compliant, polymeric layer. Thisreinforcement can tend to offset any reduced puncture resistance in theglass layer 50 e relative to the increased puncture resistance of theglass structure 90.

In stack assembly 100 e, thickness 52 e of the glass layer 50 e isgenerally smaller than the thickness 92 of the glass structure 90. Inone implementation of the stack assembly, a bend radius of ≤2 mm for thestack assembly 100 e is feasible with a thickness 52 e of approximately20 to 25 μm. To obtain such thickness levels for thickness 52 e, whileholding the thickness 92 at a higher value to maintain punctureresistance, a selective etching process can be conducted on the stackassembly 100 e.

In one example selective etching process, one step is to provide a glassstructure with a substantially constant thickness equal to the thickness92 for the glass structure 90. Coating materials are then applied on thesecond primary surface 56 e of the glass structure 90 in regionsadjacent to the intended central region 96 of the glass structure 90(i.e., the region that will be etched to the thickness 52 e) to protector otherwise mask these regions during a subsequent etching step. Forexample, these materials may be a film or ink that can be coated on theglass structure 90 by lamination or screen printing processes. One ofordinary skill in the art would readily understand what type of coatingmaterials would be suitable for a particular etchant compositionselected for the selective etching process for stack assembly 100 e. Byapplying these coating materials or the like adjacent to the centralregion 96, only the central region 96 will be exposed to the acidemployed in a subsequent etching step. In the subsequent etching step orsteps, etching solutions according to the foregoing (e.g., 15 vol % HFand 15 vol % HCl) can be applied to the masked, glass structure for anappropriate time to achieve the desired thickness 52 e in the glasslayer 50 e. After the selective etching has been completed (includingwashing off the etching solution with deionized water, for example), themasking materials can be peeled or otherwise stripped using a suitablestripper solution depending on the particular masking materials employedin the selective etching process.

Referring again to the selective etching process employed to produce astack assembly 100 e, the edges 98 can be left uncoated during theetching step or steps. As a result, these edges 98 are subjected to alight etch as the glass layer 50 e is formed with a thickness 52 e. Thislight etch to edges 98 can beneficially improve their strength. Inparticular, cutting or singling processes employed to section the glassstructure before the selective etching process is employed can leaveflaws and other defects within the surface of the glass structure 90.These flaws and defects can propagate and cause glass breakage duringthe application of stresses to the stack assembly 100 e from theapplication environment and usage. The selective acid etching process,by virtue of lightly etching these edges 98, can remove at least some ofthese flaws, thereby increasing the strength and/or fracture resistanceof the edges of the stack assembly 100 e.

In the stack assembly (or glass article) 100 e, the glass layer 50 e canbe characterized by: (a) an absence of failure when the layer 50 e isheld at a bend radius from about 1 mm to about 5 mm for at least 60minutes at about 25° C. and about 50% relative humidity; (b) a punctureresistance of greater than about 1.5 kgf when the second primary surface56 e of the layer 50 e is supported by (i) an approximately 25 μm thickpressure-sensitive adhesive having an elastic modulus of less than about1 GPa and (ii) an approximately 50 μm thick polyethylene terephthalatelayer having an elastic modulus of less than about 10 GPa, and the firstprimary surface 54 e of the layer 50 e is loaded with a stainless steelpin having a flat bottom with a 200 μm diameter; and (c) a pencilhardness of greater than or equal to 8H. In some aspects, the thickness92 of the glass structure 90 may be equal to or greater than 125 μm. Inan additional aspect, the thickness 52 e of the glass layer 50 e may beset from about 20 μm to about 125 μm to achieve the bend radius.According to an exemplary embodiment, the thickness 52 e of the glasslayer 50 e can be set from about 20 μm to about 30 μm to achieve thebend radius from about 1 mm to about 5 mm. In some aspects, thethickness 52 e of glass layer 50 e (having an alkali-freealumino-borosilicate glass composition, for example) can be about 25 μmor less to obtain a bend radius of about 2 mm, and a bend radius ofabout 1 mm with some additional light etching.

The stack assemblies 100-100 e depicted in FIGS. 1-4B can be fabricatedaccording to a method that includes the steps: forming a first glasslayer 50 a, 50 e having a first primary surface 54 a, 54 e, acompressive stress region 60, 60 a, 60 b extending from the firstprimary surface 54 a of the glass layer 50 a to a first depth 62, 62 a,62 b in the glass layer 50 a (i.e., for stack assemblies 100-100 d), anda final thickness 52 a, 52 e. As it relates to stack assemblies 100-100d (see FIGS. 1-3B), the compressive stress region 60, 60 a, 60 b isdefined by a compressive stress of at least about 100 MPa at the firstprimary surface 54 a of the layer 50 a.

The method for forming stack assemblies 100-100 e depicted in FIGS. 1-4Bcan also include the step of forming a glass element 50 having athickness 52 from about 25 μm to about 125 μm. Here, the element 50further comprises the glass layer 50 a, 50 e a first primary surface 54,and a second primary surface 56. In these aspects, the glass element 50or glass layer 50 a, 50 e can also characterized by: (a) an absence offailure when the element 50 or glass layer 50 a, 50 e is held at a bendradius 40 from about 3 mm to about 20 mm for at least 60 minutes atabout 25° C. and about 50% relative humidity; (b) a puncture resistanceof greater than about 1.5 kgf when the second primary surface 56 of theelement 50 is supported by (i) an approximately 25 μm thick PSA havingan elastic modulus of less than about 1 GPa and (ii) an approximately 50μm thick PET layer having an elastic modulus of less than about 10 GPa,and the first primary surface 54, 54 a, 54 e of the element 50 or glasslayer 50 a, 50 e is loaded with a stainless steel pin having a flatbottom with a 200 μm diameter; and (c) a pencil hardness of greater thanor equal to 8H. In other aspects of the method, glass element 50 orglass layer 50 a, 50 e can be configured to avoid failure for bend radiithat range from about 3 mm to about 10 mm. In some aspects, the bendradius 40 can be set in a range from about 1 mm to about 5 mm. The bendradius 40 can also be set to a range from about 5 mm to 7 mm withoutcausing a failure in the glass element 50 or glass layer 50 a, 50 eaccording to other aspects of the method.

In some aspects of the foregoing method, the step of forming the firstglass layer 50 a, 50 e employs one or more of the following formingprocesses: fusion, slot drawing, rolling, redrawing or float. Otherforming processes can be employed depending on the final shape factorfor the glass layer 50 a, 50 e and/or the intermediate dimensions of aglass precursor used for the final glass layer 50 a, 50 e.

The forming process is further configured to form the glass layer 50 a,50 e to the final thickness 52 a, 52 e and, as such, may includesub-process steps to obtain the final thickness 52 a, 52 e. The step offorming the first glass layer 50 a, 50 e can include a material removalprocess that is configured to remove material from the glass layer 50 a,50 e to reach the final thickness 52 a, 52 e. Various known acidetching/acid thinning processes can be employed for this purpose asunderstood by those with ordinary skill in this field. For example, asuitable etching solution can comprise 15 vol % HF and 15 vol % HCl. Bycontrolling etching time and/or etching solution concentration, adesired final thickness 52 a, 52 e can be obtained in the glass layer 50a, 50 e. An example etching rate using this solution is about 1.1 μm perminute. In some aspects of the method, the material removal processemployed to reach the final thickness 52 a, 52 e can be furtherconfigured to reduce the maximum flaw size in proximity to the firstprimary surface 54 a—e.g., to 5 μm or less, 2.5 μm or less, 0.5 μm orless, or even lower.

According to a further aspect of the method of making the stackassemblies 100-100 d depicted in FIGS. 1-3B, an ion exchange process canbe employed to generate the compressive stress region 60 a. As outlinedearlier, the step of forming a compressive stress region 60 a extendingfrom the first primary surface 54 a of the glass layer 50 a to a firstdepth 62 a can include the following additional sub-process steps:providing a strengthening bath comprising a plurality of ion-exchangingmetal ions selected so as to produce compressive stress in the glasslayer 50 a containing ion-exchangeable metal ions; and submersing theglass layer 50 a in the strengthening bath to exchange a portion of theplurality of ion-exchangeable metal ions in the glass layer 50 a with aportion of the plurality of the ion-exchanging metal ions in thestrengthening bath to form a compressive stress region 60 a that extendsfrom the first primary surface 54 a to the first depth 62 a in the glasslayer 50 a. In some aspects of the method, the ion-exchanging metal ionshave an atomic radius that is larger than the atomic radius of theion-exchangeable metal ions contained in the glass layer 50 a. In otheraspects of the method, the submersing step includes submersing the glasslayer 50 a in the strengthening bath at about 400° C. to about 450° C.for about 15 minutes to about 180 minutes to develop the compressivestress region 60 a.

According to one aspect, 75 μm thick glass samples with a compositionconsistent with Corning® Gorilla Glass® 2.0 were subjected to an ionexchange process that included a KNO₃ bath submersion at 430° C. for 30minutes. Compressive stress (MPa) as a function of glass layer depth(μm) was then measured and the results are depicted in FIG. 6A. Asshown, this ion exchange process produced compressive stress of about889 MPa at the surface of the glass and appreciable compressive stresslevels were measured to a depth of about 11.4 μm (i.e., DOL=11.4 μm).

In some aspects of the method, a post-ion exchange process to removematerial from the surface of the glass layer 50 a can provide a benefitin terms of flaw size reduction. In particular, such a removing processcan employ a light etching step to remove about 1 μm to about 5 μm fromthe final thickness of the glass layer 52 a at the first primary surface54 a after formation of the compressive stress region 60 a. For example,the removing step can employ a 950 ppm F⁻ ion (e.g., an HF acid), 0.1Mcitric acid etching solution for ˜128 minutes for this purpose. Asoutlined earlier in connection with Equation (2), a reduction in themaximum flaw size in the glass layer 50 a and/or the glass element 50,particularly near their surfaces, can serve to reduce the stressintensity factor produced from bending the layer and/or the element.

Referring to FIG. 6B, the effect on compressive stress in the glasslayer subjected to both an ion exchange and post-ion exchange materialremoval process can be observed. In particular, FIG. 6B depictscompressive stress as a function of glass layer depth (μm) for glasslayer samples prepared in accordance with those in FIG. 6A andadditionally subjected to light etching process to remove about 1-2 μmof material from the surface. These samples were measured with acompressive stress of about 772 MPa at the surface of the glass andappreciable compressive stress levels were measured to a depth of about9.6 μm (i.e., DOL=9.6 μm). In effect, FIG. 6B has a similar compressivestress as a function of depth relationship as shown in FIG. 6A; however,it is apparent that FIG. 6B is effectively a truncated version of FIG.6A, with the first portion removed consistent with the actual removal ofmaterial from the light etching process. As such, the post-ion exchangematerial removal process can somewhat reduce the DOL and maximumcompressive stress obtained from the ion exchange process, while at thesame time providing a benefit in terms of flaw size reduction. To theextent that higher compressive stress levels and/or DOL levels arenecessary for a given application, the ion exchange process can betailored to produce compressive stress and DOL levels somewhat above thetargeted levels, given the expected effect from the post-ion exchangematerial removal process.

According to some aspects, the removing process can be conducted tocontrol the flaw distribution in the compressive stress regions 60, 60 aand/or 60 b to a maximum flaw size of 5 μm or less at the first primarysurface 54 a of the glass layer 50 a. The removing step can also beconducted such that the compressive stress regions 60, 60 a and/or 60 bcomprise a maximum flaw size of 2.5 μm or less, or even as low as 0.4 μmor less, at the first primary surface 54 a of the glass layer 50 a.According to some additional aspects of the method, the removing stepcan also be conducted to control the flaw size distribution within aregion of the glass layer 50 a that lacks the superposition of acompressive stress region 60, 60 a or 60 b. Further, variants of theremoving process can be conducted at the edges 58 b of the glass element50 to control the flaw size distribution at the edges and within edgecompressive stress regions 59 a, when present (see, e.g., FIGS. 1 and1C).

According to an embodiment, a method of making stack assemblies 100-100d is provided that comprises the steps: forming a first glass layer 50 ahaving a first primary surface 54 a, a compressive stress region 60extending from the first primary surface 54 a of the glass layer 50 a toa first depth 62 in the glass layer 50 a, and a final thickness 52 a,wherein the region 60 is defined by a compressive stress of at leastabout 100 MPa at the first primary surface 54 a of the layer 50 a; andforming a glass element 50 having a thickness 52 from about 25 μm toabout 125 μm, the element 50 further comprising the glass layer 50 a, afirst primary surface 54, and a second primary surface 56. In someaspects, the element 50 comprises one glass layer 50 a.

In an exemplary embodiment, the steps of forming the first glass layer50 a and element 50 can include a step of forming an interim thickness(e.g., about 200 μm) that exceeds the final thickness 52 a of the glasslayer 50 a (and thickness 52 of the element 50) using fusion, slotdrawing, rolling, redrawing, float or other direct glass formingprocesses. The interim glass layer 50 a (and element 50) can then beseparated, cut and/or otherwise shaped into near-final part dimensionsusing known cutting processes (e.g., water cutting, laser cutting,etc.). At this point, the interim glass layer 50 a (and element 50) canthen be etched to a final thickness 52 a (e.g., about 75 μm) accordingto the foregoing process steps. Etching to a final thickness at thisstage in the process can provide a benefit in removing flaws and otherdefects introduced from the prior glass forming and separation/cuttingsteps. Next, the glass layer 50 a and element 50 can be subjected toprocess steps for forming the compressive stress region 60 including butnot limited to the foregoing ion exchange process. A final, light etchcan then be performed on the glass layer 50 a and element 50 containingthe compressive stress region 60 according to the prior-describedprocess. This final, light etch can then remove any appreciable flawsand defects in the surface of the glass layer 50 a and element 50 thatresulted from the prior ion exchange process. The glass element 50 orglass layer 50 a produced according to the method can be characterizedby: (a) an absence of failure when the element 50 or glass layer 50 a isheld at a bend radius from about 3 mm to about 20 mm for at least 60minutes at about 25° C. and about 50% relative humidity; (b) a punctureresistance of greater than about 1.5 kgf when the second primary surface56, 56 a of the element 50 or layer 50 a is supported by (i) anapproximately 25 μm thick pressure-sensitive adhesive having an elasticmodulus of less than about 1 GPa and (ii) an approximately 50 μm thickpolyethylene terephthalate layer having an elastic modulus of less thanabout 10 GPa, and the first primary surface 54, 54 a of the element 50or layer 50 a is loaded with a stainless steel pin having a flat bottomwith a 200 μm diameter; and (c) a pencil hardness of greater than orequal to 8H.

In a further exemplary embodiment, the steps of forming the first glasslayer 50 a and element 50 to the final thickness 52 a and thickness 52,respectively, can be conducted by employing fusion, slot drawing,rolling, redrawing, float or other direct glass forming processes. Theglass layer 50 a (and element 50) can then be separated, cut and/orotherwise shaped into near-final part dimensions using known cuttingprocesses (e.g., water cutting, laser cutting, etc.). At this point, theglass layer 50 a (and element 50) can then be subjected to process stepsfor forming the compressive stress region 60 including but not limitedto the foregoing ion exchange process. A final, light etch can then beperformed on the glass layer 50 a and element 50 containing thecompressive stress region 60 according to the prior-described process.This final, light etch can then remove any appreciable flaws and defectsin the surface of the glass layer 50 a and element 50 that resulted fromthe prior ion exchange process.

The glass element 50 or glass layer 50 a produced according to themethod can be characterized by: (a) an absence of failure when theelement 50 or glass layer 50 a is held at a bend radius from about 3 mmto about 20 mm for at least 60 minutes at about 25° C. and about 50%relative humidity; (b) a puncture resistance of greater than about 1.5kgf when the second primary surface 56, 56 a of the element 50 or layer50 a is supported by (i) an approximately 25 μm thick pressure-sensitiveadhesive having an elastic modulus of less than about 1 GPa and (ii) anapproximately 50 μm thick polyethylene terephthalate layer having anelastic modulus of less than about 10 GPa, and the first primary surface54, 54 a of the element 50 or layer 50 a is loaded with a stainlesssteel pin having a flat bottom with a 200 μm diameter; and (c) a pencilhardness of greater than or equal to 8H.

Referring to FIG. 7A, a schematic plot of estimated stress intensityfactors is provided for glass layers of three compositions, “A,” “B” and“C.” The composition of the A group is: SiO₂ at 67.1% (by mol %); Al₂O₃at 6.3%; B₂O₃ at 19.9%; MgO at 0.5%; CaO at 4.8%; SrO at 0.5%; SnO₂ at0%; and Na₂O at 0.9%. The composition of the B group is: SiO₂ at 66.7%(by mol %); Al₂O₃ at 10.9%; B₂O₃ at 9.7%; MgO at 2.2%; CaO at 9.1%; SrOat 0.5%; SnO₂ at 0.1%; and Na₂O at 0%. The composition of the C groupis: SiO₂ at 67.4% (by mol %); Al₂O₃ at 12.7%; B₂O₃ at 3.7%; MgO at 2.4%;CaO at 0%; SrO at 0%; SnO₂ at 0.1%; and Na₂O at 13.7%. Equation (2) wasemployed to generate the estimates depicted in FIG. 7A. Glass layers“A,” “B” and “C” have elastic moduli of 57.4, 69.3 and 73.6 GPa,respectively. Further, glass layers “A,” “B” and “C” have a Poisson'sratio of 0.22, 0.22 and 0.23, respectively. In addition, stressintensity factor estimates were performed for the glass layers “A,” “B”and “C” having a thickness of 25, 50 and 100 μm and a bend radius of 3,5 and 7 mm. A flaw size of 400 nanometers (nm) was assumed for allcases, as it is a typical maximum flaw size for a fusion-formed glasssurface. No compressive stress region was assumed to be present in anyof these glass layers.

In FIG. 7A, regions I, II and III refer to instantaneous failure, slowfatigue failure and no-failure regions, respectively. As the estimatesindicate, increasing the bend radius and decreasing the thickness of theglass layer are steps that each tend to reduce the stress intensityfactors. If the bend radius is held to no lower than 5 mm and thethickness of the glass layer to 25 μm or less, the estimated stressintensity factors in FIG. 7A suggest that no failures would occur instatic tension or fatigue (e.g., K at <0.2 MPa√m for region III). Theseparticular glass layers depicted in FIG. 7A (i.e., glass layers with abend radius equal to or greater than 5 mm and a thickness of 25 μm orless) could be suitable for use in stack assemblies and glass articleswith relatively modest puncture resistance requirements according tocertain aspects of the disclosure.

Referring to FIG. 7B, a schematic plot of estimated stress intensityfactors is provided for glass layers of three compositions, “A,” “B” and“C” (i.e., the same compositions as employed for the glass layersdepicted in FIG. 7A). Each of the glass layers employed in the estimatesdepicted in FIG. 7B was assumed to have a thickness of 50 μm and a bendradius of 5 mm. Further, the “Control” (also denoted by A, B and C)group was assumed to lack a superimposed compressive stress region, andthe “IOX” group (also denoted by A″, B″ and C″) was assumed to possess acompressive stress region developed through an ion exchange processhaving about 700 MPa of surface compression, according to an aspect ofthis disclosure. A more conservative flaw size of 2000 nm (2 μm) wasassumed for the purpose of generating these estimates, reflecting aworst-case scenario of a large flaw introduced at the application-usestage by a customer well after fabrication of the device containing thestack assembly, glass element or glass article according to an aspect ofthis disclosure.

As the estimates in FIG. 7B indicate, a compressive stress regiondeveloped in a glass layer with an ion exchange process cansignificantly offset the stress intensity levels in the glass layersobserved upon bending. Stress intensity levels well below the region IIIthreshold (e.g., K at <0 MPa√m for region III) were observed for the“IOX” glass layers having a 50 μm thickness and a bend radius of 5 mm,by virtue of the additional compressive stress superimposed on thetensile stresses developed during bending. In contrast, the Controlgroup, without a compressive stress region, was estimated to have stressintensity levels within region I.

Referring to FIG. 8, a schematic plot is provided of estimated stresslevels at the surface of glass layers of one particular composition, aglass composition comparable to the composition of the C group depictedin FIGS. 7A and 7B. Each of the glass layers employed to generate thestress estimates depicted in FIG. 8 was assumed to have a thickness of25, 50, 75 and 100 μm and a bend radius of 5 mm. Further, some of theseglass layers were assumed to lack a compressive stress region (i.e., the“Control” group) and the remaining glass layers were assumed to possessa compressive stress region having about 700 MPa of surface compression,e.g., as developed through an ion exchange process (i.e., the “IOX”group) according to a further aspect of this disclosure. A flaw size of400 nm was assumed for all cases, as it is a typical maximum flaw sizefor a fusion-formed glass surface. Further, the safety zone (i.e.,region III) was set at stress intensity safety factor of K<0.2 MPa√m.

As the estimates in FIG. 8 indicate, a compressive stress regiondeveloped in a glass layer with an ion exchange process cansignificantly reduce the stress intensity levels in the glass layersobserved upon bending. Stress intensity levels well below the region IIIthreshold (e.g., K at <0.2 MPa√m for region III) were observed for allof the “IOX” glass layers having a thickness of 25, 50, 75 and 100 μmand a bend radius of 5 mm, by virtue of the additional compressivestress superimposed on the tensile stresses developed during bending. Incontrast, the Control group, without a compressive stress region, wasestimated to have stress intensity levels in region I for allthicknesses.

Referring to FIG. 9, a plot of failure puncture load data for glasslayers of one composition having a thickness of 75 μm and a compressivestress region developed through an ion exchange process is providedaccording to an aspect of this disclosure. In particular, the glasscomposition for the samples tested in FIG. 9 was: SiO₂ at 68.9% (by mol%); Al₂O₃ at 10.3%; Na₂O at 15.2%; MgO at 5.4%; and SnO₂ at 0.2%. All ofthe glass layers tested in the experiment used to generate the data ofFIG. 9 were subjected to an ion-exchange process to produce acompressive stress region with a compressive stress at the surface ofabout 772 MPa and a DOL of 9.6 μm. For purposes of testing, the glasslayers were laminated to a 50 μm PET layer (having an elastic modulus ofless than about 10 GPa) with a 25 μm PSA layer (having an elasticmodulus of less than about 1 GPa). Puncture testing was performed on theouter glass surface.

As shown in FIG. 9, four groups of samples were tested to develop thepuncture test data. Each group corresponded to a different puncturedevice: a 200 μm diameter, flat bottom stainless steel punch; a 0.5 mmtungsten carbide ball; a 1.0 mm tungsten carbide ball; and a 1.5 mmtungsten carbide ball. The data in FIG. 9 demonstrate the sensitivity ofthe puncture failure load data to the particular puncture deviceemployed in the testing. Generally, the variability in results appearsto be similar for each of the devices employed. As indicated in FIG. 9,the glass layers having a thickness of 75 μm with a compressive stressregion developed through ion-exchange processing had puncture failureloads well in excess of 4 kgf when tested with a 200 μm diameter, flatbottom stainless steel punch.

In another example, a glass layer with a composition that was comparableto the glass layers tested in FIG. 9 was prepared according to an aspectof this disclosure with a compressive stress region generated through anion exchange process was subjected to a 2-point, static fatigue bendtest. In particular, the glass layer tested had a thickness of 75 μm andits compressive stress region was developed by submersion in a KNO₃molten salt bath at 430° C. for 30 minutes. Further, the glass layer wassubjected to a post-ion exchange material removal process involving anacid etch in a 950 ppm F⁻ ion, 0.1M citric acid etching solution forabout 128 minutes. Upon testing, the glass layer did not fail afterbeing subjected to a bend radius of ˜5 mm for 120 hours.

In a further example, 75 μm thick glass layer samples were prepared inaccordance with the composition and ion exchange process steps of thesamples tested in FIG. 9. These samples were not laminated with anycompliant layers. As-prepared, these samples were 105×20×0.075 mm. 10samples were then arranged in a bent configuration within a static testfixture with a 10 mm plate separation (plates fabricated from Teflon®material). The samples were then held within the fixture at 85° C. under85% relative humidity. 9 of the 10 samples have not experienced anyfailure modes after over two months of testing in the fixture. Onesample failed during the first day of testing. Given these results andother analyses, it is believed that any samples with failure-inducingsurface flaws remaining after processing can be removed through prooftesting.

In an additional example, 75 μm thick glass layer samples were preparedin accordance with the composition and ion exchange process steps of thesamples tested in FIG. 9, including lamination to a 50 μm PET layer witha 25 μm PSA layer. As-prepared, these samples were 105×20×0.075 mm (notincluding the PET/PSA layers). Five samples were then subjected to aclamshell cyclic fatigue test. The clamshell cyclic fatigue test fixtureheld the samples with a 10 mm plate separation under ambient temperatureand humidity conditions. Each cycle involved closing the clamshellfixture while retaining the 10 mm plate separation and then fullyopening the fixture such that the sample was uniform with no bend. Eachof the five samples has survived over 45,000 of such cycles.

Referring now to FIG. 10, a schematic plot of estimated stress intensityfactors for glass layers of three compositions, groups “A,” “B” and “C”having the same composition as the groups of samples employed for theestimates given in FIGS. 7A and 7B, is provided according to a furtheraspect of the disclosure. Each of the samples employed for the estimatesin FIG. 10 had a thickness of 25, 50, 75 or 100 μm, and a bend radius of10 or 20 mm. Here, each tested sample possessed compressive stressregions that were developed through heating, and subsequently cooling,core and cladding regions of the glass layers in intimate contact, thecore region having a CTE greater than the CTE of the clad regions. Theestimates employed in FIG. 10 assumed a flaw size of about 2 μm in thesurface of the glass layer for each sample. Further, it was assumed thatabout 150 MPa of compressive stress was developed in the compressivestress region of these glass layers through CTE mismatch between thecore and cladding regions.

As the estimates in FIG. 10 indicate, a compressive stress regiondeveloped in a glass layer with a CTE mismatch between its core andcladding regions can significantly reduce the stress intensity levels inthe glass layers observed upon bending. Stress intensity levels wellbelow the region III threshold (e.g., K at <0.2 MPa√m for region III)were observed for all of the glass layers having a thickness of 25, 50,75 and 100 μm and a bend radius of 20 mm, by virtue of the additionalcompressive stress superimposed on the tensile stresses developed duringbending. In addition, glass layers having a thickness of 25 and 50 μmand a bend radius of 10 mm also possessed stress intensity levels belowthe region III threshold. As such, these particular glass layersemploying a CTE mismatch approach can be employed according to aspectsof the disclosure within stack assemblies and glass articles having bendradii requirements of 10 mm or more (see, e.g., stack assembly 100 b inFIG. 1D and the corresponding description).

In FIG. 11, a Weibull plot of failure probability vs. puncture load datafor glass layers of one composition having a thickness of 75 μm and acompressive stress region developed through an ion exchange process isprovided according to an aspect of this disclosure. In particular, theglass composition for the samples tested was comparable to those testedin FIG. 9. All of the glass layers tested in the experiment used togenerate the data of FIG. 11 were subjected to an ion-exchange processto produce a compressive stress region with a compressive stress at thesurface of about 772 MPa and a DOL of 9.6 μm. The “B” group of glasslayers, as denoted by open circle symbols in FIG. 11, consisted of glasssamples laminated to a 50 μm PET layer with a 25 μm PSA layer. Allpuncture testing was performed on the outer glass surface of thesesamples, away from the PET/PSA layer stack. An “A” group of glasslayers, as denoted by closed circle symbols in FIG. 11, consisted ofglass samples that were not laminated to a PET/PSA layer stack. Thepuncture test results shown in FIG. 11 were generated using a 200 μmdiameter, flat bottom stainless steel punch.

As shown in FIG. 11, the non-laminated “A” group and laminated “B” groupof samples exhibited Weibull characteristic strength values (i.e., at afailure probability of 63.2% or greater) of 4.3 kgf and 3.3 kgf,respectively. Further, all samples from both groups failed at 5.5 kgf orgreater. The Weibull modulus of the laminated “B” group is higher thanthe Weibull modulus of the non-laminated “A” group, indicating thatvariability in failure performance can be reduced by virtue oflaminating the samples. On the other hand, the non-laminated “A” groupdemonstrated a higher average puncture failure load and Weibullcharacteristic strength compared to the laminated “B” group, suggestingthat lamination can somewhat reduce puncture test performance, likelycaused by increased local stress concentrations associated with thecompliant layers in vicinity to the glass near the puncture testing tip.As such, the choices and options associated with laminating stackassemblies according to aspects of this disclosure can be mindful of thepotential optimization of puncture resistance variability and overallmaximization of puncture resistance.

Overall Stress Profile

Tensile stress in glass tends to make flaws propagate, whereascompressive stress in glass tends to suppress the propagation of flaws.Flaws may be present in the glass from the nature in which it was made,handled, or processed. Accordingly, it is desirable to have the portionsof the glass that are likely to have or receive flaws (i.e., the primarysurfaces, and from those surfaces to a depth to which cracks maypenetrate) in compression. For a bent piece of glass, the stress profileis comprised of two main components, the first σI being that inherentlyin the glass from the way it was made and/or processed, and the secondσB being that induced from a bend in the glass.

One example of the first component σI, stress inherently in the glassitself, is shown in FIG. 12. Line 1202 is a stress profile for a 75micron thick glass element made of Corning Code 2319 (Gorilla® Glass 2)having a compressive stress of 756 MPa and a DOL of 9.1 microns. As usedherein, a positive stress is tensile, and a compressive stress isnegative. The inherent stress profile in the glass may vary based ondifferent IOX conditions, glass compositions, and/or differingprocessing conditions when making the glass (as in the case of glasslaminates described above, which may impart a compressive stress in theouter layer of the glass). In any event, the glass itself will have aninherent stress profile.

When the glass element 50 is bent, the bend induces a second stresscomponent σB to the stress profile within the glass. For example, whenglass element 50 is bent in the direction shown in FIG. 1A, tensilestress induced by the act of bending is given by Equation (1) above, andwill be the maximum at the outer surface, for example first primarysurface 54 of glass element 50. The second primary surface 56 will be incompression. An example of bend induced stress is shown in FIG. 13. asline 1302. Line 1302 is a bend stress plot for a 75 micron thick glasselement made of Corning Code 2319 (Gorilla® Glass 2) but, for themoment, ignoring the inherent stress profile in the glass due to IOX.The parameters for Equation (1), for this type of glass, as plotted, aremodulus E=71.3 GPa, poissons ratio v=0.205, thickness=75 microns, andbend radius=4.5 mm.

Thus, the overall stress profile in the glass will be, again, the sum ofthe two above-described components, or σI+σB. The overall stress isshown in FIG. 14 as solid line 1402, which is the sum of line 1202inherent stress, σI, shown in short dashes, and line 1302 bend inducedstress σB shown in long dashes. The stress at the outer surface of theglass element 50, for example primary surface 54 as shown in FIG. 1A, isshown at the left side of the plot, whereas the stress at the innerprimary surface 56 is shown at the right side of the plot. As can beseen from line 1402, the stress at the inner second primary surface 56is compressive and will limit the propagation of flaws. Also, at thestress at the outer or first primary surface 54 is also compressive andwill limit the propagation of flaws. As shown, for the conditions notedabove, the compressive stress extends from the first primary surface 54to a depth of a few microns. The amount of compressive stress at outerprimary surface, and the depth below the outer primary surface to whichthe compressive stress extends, can be increased in a number of ways.First, the bend induced tensile stress may be made smaller. As can beseen from Equation (1) the bend induced stress σB can be made smaller byusing a thinner glass, and/or a larger bend radius, and/or a glass witha lower modulus E, and/or a glass with a higher poissons ratio v.Second, the amount of compressive stress at the outer primary surfacecan be increased by choosing a glass with a greater inherent compressivestress σI at the desired location as by, for example, using differentIOX conditions, glass compositions, and/or differing processingconditions, as noted above in connection with the discussion on FIG. 12.

An important aspect of the disclosure is that at the outer primarysurface, i.e., the primary surface at the outside of a bent portion ofglass element 50, for example first primary surface 54 as shown in FIG.1A, for a foldable or rollable display wherein the bend radius is ≤20mm, the sum of the inherent stress σI and the bend stress σB is lessthan 0 as shown by Equation (3) below.σI+σB<0  Equation (3)

Additionally, it is further beneficial to define the stress profile inthe glass element so that Equation (3) is satisfied to a depth of atleast 1 micron below the primary surface 54 in some examples, to a depthof at least 2 microns below the primary surface 54 in other examples,and to a depth of at least 3 microns below the primary surface 54 instill other examples. The deeper below the primary surface that Equation(3) holds, the more durable the device will be. That is, if a flaw (ascratch from handling the device during manufacturing or use, forexample) extends below the primary surface to a greater degree than therelationship in Equation (3) holds, then the flaw will propagate overtime and the glass element will fail. Stated another way, the IOXprofile should be managed so that the stress induced from bending plusthe inherent stress produces a region 1403, i.e., line 1402 interceptsthe Y axis at zero or less, to minimize failure. Additionally, infurther examples, the flaw population should be managed so that flawsare contained in the region 1403, i.e., the maximum flaw depth from theglass surface does not exceed the point at which the line 1402intercepts the X axis whereby the flaw is contained in the compressiveregion in the glass and will not propagate. Thus, by maximizing the area1403, smaller bend radii and deeper flaws may be tolerated while failureis minimized.

The outer primary surface was shown as first primary surface 54 in theforegoing discussion, but in some examples the second primary surface 56may be the outer primary surface instead of first primary surface 54. Inother examples, for example in a tri-fold arrangement, both the firstprimary surface 54 and the second primary surface 56, may have portionsthat are an outer primary surface, i.e., are on the outside of a bentportion of the glass element 50.

Benefit of Light Etch Step after IOX

The benefit of performing an etching step after an IOX strengtheningstep is shown in FIGS. 15 and 16, which show various two point bendstrength distributions. The two point bend values in these figures weremeasured by testing the samples as follows. The samples were stressed ata constant rate of 250 MPa/sec. For the two point bending protocol, seeS. T. Gulati, J. Westbrook, S. Carley, H. Vepakomma, and T. Ono, “45.2:Two point bending of thin glass substrates,” in SID Conf., 2011, pp.652-654. The environment was controlled at 50% relative humidity and 25°C. The data sets show the maximum stress at failure, and assume that thefailure occurs at the minimum radius location. Line 1501 shows a Weibulldistribution for strength of glass samples that were deep etched from200 microns thick to 75 microns thick (no IOX or subsequent etching wereperformed on these samples). This set of samples shows a strength ofabout 850 MPa at a B10 failure probability. Line 1502 shows a Weibulldistribution of strength of glass samples that were deep etched from 200microns thick to 75 microns thick and then subject to IOX (but nosubsequent etching). These samples show a slightly decreased strength,of about 700 MPa at a B10 failure probability, from the values for thedeep-etched-only samples of Line 1501. Not wishing to be bound bytheory, it appears that the IOX process reduces strength by extendingflaws. Line 1503 then shows a Weibull distribution of strength of glasssamples that were deep etched from 200 microns thick to 75 micronsthick, subject to IOX under the same conditions as the samples of Line1502, and then given a subsequent light etching to remove <2 microns ofthickness from each surface. These samples show an increased strength,of about 1500 MPa at a B10 failure probability, with respect to each ofthe sample sets of Line 1501 and 1502. FIG. 15 thus shows the benefitsof performing a light etch after the IOX. Again, not wishing to be boundby theory, it is believed that the light etch after IOX reduces flawdepth and blunts crack tips introduced by the IOX process itself and,thus, increases the strength of the samples.

Although IOX appears to reduce the strength in deep-etched samples (asseen in FIG. 15), FIG. 16 shows another benefit (in addition to thatdiscussed above in connection with FIGS. 12-14) of strengthening theprimary surfaces of the glass for foldable and/or rollable displays. Inparticular, non-IOXed glass is subject to fatigue by not having itsouter surface (of a bend) in compression. Accordingly, non-IOXed glasssamples are more likely to see time delayed failure. Line 1601 shows aWeibull distribution of strength of glass samples that were only deepetched from 200 microns thickness to 75 microns thickness (these werenot IOXed), and that were subject to 2 point bend strength testingfollowing a very low load 10 gf contact with a cube corner diamondindenter. The cube corner test was performed on a Mitutoyo HM-200Hardness Testing Machine with a cube corner diamond indenter tip. Thetest was performed on bare glass placed on the sample stage of theapparatus. The load of 10 grams force (go was applied and held for adwell time of 10 seconds. The indentation was performed in 50% relativehumidity and 25° C. The indent is centered in the testing sample, sothat this will be the location of maximum stress (minimum radius) whentesting by two point bend test. Following indentation, the samples wereheld in the same environment for 24 hours prior to the two point bendtest as described above. The line 1601 shows a strength of about 150 MPaat a B10 failure probability. Line 1603 shows a Weibull distribution ofstrength of glass samples that were deep etched from 200 micronsthickness to 75 microns thickness, were IOXed, subsequently etched toremove 2 microns thickness from each side, and then were subject to 2point bend strength testing following a very low load 10 gf contact witha cube corner diamond indenter. The line 1603 shows as strength of about800 MPa at a B10 failure probability. By comparing line 1601 with Line1501, and by comparing Line 1603 with line 1503, it is seen that anycontact will greatly reduce the strength of a non-strengthened part.However, by comparing Line 1603 with Line 1601, it is seen that thedamage is contained within the compression depth for the IOXed part,giving greater strengths for the strengthened parts of Line 1603 thanfor the non-strengthened parts of Line 1601. Accordingly, strengthening,by IOX for example, is s beneficial manner of reducing the effects ofcontact damage, even contact damage caused by relatively low loads of 10gf.

Vickers Crack Initiation

Examples of glass elements according to the present disclosure are alsocapable of providing resistance to the formation of strength limitingflaws. This is beneficial when the glass element is used as a coverglass and subject to contact as from a user, or other contact event.Although not wishing to be bound by theory, IOX also provides resistanceto the formation of strength-limiting flaws. A force of greater than 2kgf is necessary to produce/initiate a crack of >100 microns in samplesof glass that have been deep-etched, IOXed, and then light etched, asdiscussed above. FIGS. 17-20 show a comparison between samples FIGS. 17and 18 that were IOXed (subject to deep-etch, IOX, and then light etchas discussed above) and those in FIGS. 19 and 20 that were not IOXed(but were simply deep etched). FIG. 17 shows an IOXed sample that wassubject to a 1 kgf load with a Vickers diamond indenter. The Vickerscrack initiation test was performed on a Leco Vickers Hardness TesterLV800AT. The test was performed on bare glass placed on the sample stageof the indentation apparatus. The glass was indented at increasing loaduntil more than 50% of ten indents made at a given load showed thepresence of strength limiting flaws. The indentation was performed underambient conditions with an indent dwell time of 10 seconds. As seen inFIG. 17, the indenter produced a flaw of less than 100 microns. FIG. 18shows an IOXed sample that was subject to a 2 kgf load with a Vickersindenter. Similarly to FIG. 17, the indenter produced a flaw of lessthan 100 microns. Accordingly, it is seen that examples of the presentdisclosure can withstand a 2 kgf load without incurring a strengthlimiting flaw, i.e., a flaw of greater than 100 microns. FIG. 19 shows anon-IOXed glass sample that was subject to a 1 kgf load with a Vickersindenter. As seen in FIG. 19, the indenter produced a flaw of greaterthan 100 microns. FIG. 20 shows a non-IOXed glass sample that wassubject to a 2 kgf load with a Vickers indenter. As seen in FIG. 20, theindenter produced a flaw of much greater than 100 microns. A comparisonof FIG. 17 with FIG. 19, and a comparison of FIG. 18 with FIG. 20, showsthat the IOXed glass parts are able to provide resistance to theformation of strength limiting flaws, i.e., of flaws greater than 100microns. As can be seen by a comparison of FIGS. 18 and 20, a very smallincrease of force on the Vickers indenter (i.e., from 1 kgf to 2 kgf)produces a much larger flaw in the non-strengthened part. Although notwishing to be bound by theory, it is thought that the Vickers indenterrequires much more force (than does the cube corner) to producestrength-limiting flaws because the Vickers indenter has a much widerangle than does the cube corner indenter.

Vickers Hardness

The glass element has a Vickers Hardness of from 550 to 650 kgf/mm2. TheVickers hardness was measured on a Mitutoyo HM-114 Hardness TestingMachine. The hardness was measured by indenting at 200 grams force (gf)and measuring the average of the two major diagonal lengths of theresulting impression. The hardness was calculated by the followingequation: VHN=(P*1.8544)/d2, where VHN is Vickers hardness number, P isthe applied load of 200 gf, and d is the average major diagonal length.Typically ten VHN measurements are taken to determine the average VHN.Indentation is performed in 50% relative humidity and 25° C. The test isperformed on bare glass placed on the sample stage of the indentationapparatus. The dwell time of the indentation is 10 seconds. Hardness,including Vickers Hardness, is a measure of permanent deformation in amaterial. The harder a material, as evidenced by a higher VickersHardness number, the less the permanent deformation in the material.Accordingly, hardness is a measure of scratch and other damageresistance of the material to, for example, keys, and things of similaror lesser hardness that may come into contact with the material. AVickers Hardness of from 550 to 650 kgf/mm2 provides suitable scratchand other damage resistance of a device cover to keys and other objectsthat may be found in a user's pocket or backpack, for example, togetherwith the device cover.

Closing Force

Another consideration in a foldable or bendable display is the force toget the device to fold or bend. The force necessary to close the deviceshould not be so high as to make the user uncomfortable when closing it.Additionally, the force should not be so high as to tend to make thedevice want to open when it is intended to stay closed. Accordingly, thetwo point bend closing force should be limited. However, because the twopoint bend closing force also depends upon the dimension of the glasselement extending along the direction of the fold line, herein calledwidth, the forces should be normalized based on width. The two pointbend closing force is given by Equation (4) below, which assumes thatthe glass will behave as if it were disposed between two parallelplates, i.e., so that it does not have a constant bending radius. The(1−v²) term under the modulus takes into account that for a materialsuch as glass, a stress/bend in one direction will produce a shrinkingin another direction. This is typically the case for plate-shapedobjects.

$\begin{matrix}{F = {\left( \frac{wt}{6} \right)\left( \frac{\sigma_{m\;{ax}}^{2}}{\left( \frac{E}{1 - v^{2}} \right)} \right)}} & {{Equation}\mspace{14mu}(4)}\end{matrix}$

wherein t is the thickness of the sample in mm, w is the width in mm ofthe glass element along the fold line, E is the modulus of the glassmaterial in GPa, v is the poissons ratio of the material, and whereinσmax is given by the following equation (5) when using the parallelplate two point bend method.

$\begin{matrix}{\sigma_{{ma}\; x} = {1.198\;{\frac{E}{1 - v^{2}}\left\lbrack \frac{t}{\left( {D - t} \right)} \right\rbrack}}} & {{Equation}\mspace{14mu}(5)}\end{matrix}$wherein E is the modulus of the material in GPa, v is the poissons ratioof the material, t is the thickness of the material in mm, and D is theseparation distance (in mm) between the parallel plates. Equation (5) isthe maximum stress in a parallel plate bend apparatus, and is differentfrom that in Equation (1) because it accounts for the fact that thesample will not achieve a uniform constant bend radius (as was assumedfor Equation (1)) in the test apparatus, but will have a smaller minimumradius. The minimum radius (R) is defined as D−h=2.396 R, wherein h isthe glass thickness in mm and is the same as t. The minimum radius R,determined for a given plate separation can be used in Equation (1) todetermine maximum stress.

Dividing each side of equation (4) by w, width of the glass elementalong the fold line, leads to a value for F/w. Plugging in values forthe glass samples found by the inventors to have particularly beneficialclosing force—thickness t=0.075 mm, a plate separation distance D=10 mm(wherein plate separation distance is that in a two point bend methodvia parallel plates as discussed below in connection with the cycletesting), a modulus E of 71 GPa, a poissons ratio v of 0.205—theinventors have found that a value of F/w of 0.076 N/mm or less leads toan acceptable closing force, i.e., one that is not uncomfortable to auser, and one that does not tend to make the device open when in itsfolded state. By way of example, the inventors found that with a widthof 105.2 mm, a closing force of 7.99N was acceptable. And with a widthof 20 mm, a force of 1.52 N was acceptable. Thus, again, normalizing forwidth, a value F/w=0.076 N/mm or less was found to be acceptable.

Cycle Test

During use in a display or other device, the glass element 50 may besubject to repeated bending cycles. For example, the display device maybe repeatedly folded and unfolded. Thus, to determine a suitablelifetime of the device, it is beneficial to characterize the number ofcycles that the glass element may be folded and unfolded. To test thecyclic bending durability of glass element 50, the glass element 50 wasdisposed in a curved shape between two parallel plates 2102 and 2104(See FIG. 21) having an initial separation distance D of 30 mm. Theplates were then moved, while remaining parallel, so as to decrease theseparation distance to a target distance, held at that target distancefor about a second, and then returned to the initial separation distanceof 30 mm, held at the initial separation distance for about a second,thus ending a cycle. The plates were moved at a rate of 38 mm/s. Thecycle is then repeated. The number of cycles may then be counted untilthe glass element fails. Although an initial separation distance D of 30mm was chosen, in other tests, the initial separation distance may begreater or less than 30 mm. The value of 30 mm was chosen as a distanceat which there would not be significant load on the glass element 50.The target distance can be varied so as to achieve a target bend radiusthat one desires to test. The target bend radius (being the tightestradius achieved by the glass element being tested) is equal to 0.414times the separation distance D of the parallel plates 2102, 2104. Thisis a simplified calculation that essentially ignores the glass thicknessh (or t) from the calculation of minimum bending radius R in thediscussion following Equation (5) because the glass thickness ofinterest will typically be much less than the plate separation distanceD. However, to the extent necessary, the glass thickness can beaccounted for by using the calculation for minimum bending radius R inthe discussion following Equation (5) above. The bend radius is notsimply half of D because the glass element does not form a perfectsemicircle in the test apparatus. Thus, to test different target bendradii, different parallel plate distances can be suitably calculated. Asshown, first primary surface 54 makes the outer surface of the bend andcontacts with the inner surfaces of the parallel plates, whereas secondprimary surface 56 forms the inner surface of the bend. When a secondlayer 70 is present on first primary surface 54, such would be incontact with the parallel plates. Because the thickness of second layer70 is typically minimal (on the order of 1 micron or less) its thicknessmay be ignored when calculating bend radius (for first primary surface54, as shown in FIG. 21) from plate separation distance D. However, tothe extent that second layer 70 has any significant thickness, the plateseparation distance D may be increased by twice the second layerthickness in order to achieve a desired target bend radius at theprimary surface being tested (as shown in FIG. 21, first primary surface54). Although first primary surface 54 is shown as being the outerprimary surface of the bent configuration of element 50, a similarmethod may be used to test bend radius and cycling with second primarysurface 56 as the outer surface of the bend, as appropriate to theconfiguration which glass element 50 will take in an end device.

A glass element according to one example of the present disclosure was75 microns thick, had an IOX compressive stress of 775 MPa, and a DOL of10 microns, and withstood over 200,000 bending cycles at a target plateseparation distance D of 9 mm, as described above. Another glass elementaccording to another example of the present disclosure was 75 micronsthick, had an IOX compressive stress of 775 MPa, and a DOL of 10microns, and withstood over 200,000 bending cycles at a target plateseparation distance D of 8 mm, as described above. For a typical displaydevice, passing 200,000 bending cycles is considered a suitablelifetime.

Still further, although a dynamic bending test is described above, asimilar parallel plate test apparatus may be used to test a static bendradius. In this case, the parallel plates 2102, 2104 are set to adesired separation distance D so that 0.414 times the plate separationdistance equals the desired static bend radius to be tested. Once theparallel plates 2102, 2104 are set at the necessary separation distanceD, the glass element is placed between the parallel plates so as toachieve a bent configuration as shown in FIG. 21.

CONCLUSION

It will be apparent to those skilled in the art that variousmodifications and variations can be made without departing from thespirit or scope of the claims. For example, although a compressivestress region 60 in the stack assembly 100 (see FIGS. 1, 1A) was shownand described as extending from the first primary surface 54 a into theglass layer 50 a, a similar compressive stress region may be includedextending from the second primary surface 56 a into the glass layer 50a. Also, for example, although the center of a bend radius was shown asbeing on the same side of the stack assembly 100 as the second primarysurface 56 a, such need not be the case. Instead, or in additionthereto, the center of a bend radius may be disposed on the same side ofthe stack assembly 100 as the first primary surface 54 a. A center of abend radius may be disposed on each side of the stack assembly 100 aswhen, for example, the stack is put in a tri-fold configuration.Further, for example, there may be disposed more than one center of abend radius disposed on one side of the stack assembly according toother manners of folding the stack assembly. Still further, for example,although only one bend radius was shown in any one particular example,any suitable and/or practical number of bend radii may be present in thestack assembly.

According to a first exemplary aspect, a stack assembly is provided thatcomprises: a glass element having a thickness from about 25 μm to about125 μm, a first primary surface, and a second primary surface, the glasselement further comprising: (a) a first glass layer having a firstprimary surface; and (b) a compressive stress region extending from thefirst primary surface of the glass layer to a first depth in the glasslayer, the region defined by a compressive stress of at least about 100MPa at the first primary surface of the layer. The glass element ischaracterized by: (a) an absence of failure when the element is held ata bend radius from about 3 mm to about 20 mm for at least 60 minutes atabout 25° C. and about 50% relative humidity; (b) a puncture resistanceof greater than about 1.5 kgf when the second primary surface of theelement is supported by (i) an approximately 25 μm thickpressure-sensitive adhesive having an elastic modulus of less than about1 GPa and (ii) an approximately 50 μm thick polyethylene terephthalatelayer having an elastic modulus of less than about 10 GPa, and the firstprimary surface of the element is loaded with a stainless steel pinhaving a flat bottom with a 200 μm diameter; and (c) a pencil hardnessof greater than 8H.

The assembly of the first exemplary aspect, wherein the glass layercomprises an alkali-free or alkali-containing aluminosilicate,borosilicate, boroaluminosilicate, or silicate glass composition.

The assembly of any one of the preceding first exemplary aspects,wherein the thickness of the element is from about 50 μm to about 100μm.

The assembly of any one of the preceding first exemplary aspects,wherein the thickness of the element is from about 60 μm to about 80 μm.

The assembly of any one of the preceding first exemplary aspects,wherein the bend radius of the element is from about 3 mm to about 10mm.

The assembly of any one of the preceding first exemplary aspects,wherein the bend radius of the element is from about 5 mm to about 7 mm.

The assembly of any one of the preceding first exemplary aspects,wherein the compressive stress at the first primary surface of the glasslayer is from about 600 MPa to 1000 MPa.

The assembly of any one of the preceding first exemplary aspects,wherein the first depth is set at approximately one third of thethickness of the glass layer or less from the first primary surface ofthe glass layer.

The assembly of any one of the preceding first exemplary aspects,wherein the first depth is set at approximately 20% of the thickness ofthe glass layer or less from the first primary surface of the glasslayer.

According to a second exemplary aspect, a stack assembly is providedaccording to the first exemplary aspect, further comprising: a secondlayer having a low coefficient of friction disposed on the first primarysurface of the glass element.

The assembly according to the second exemplary aspect, wherein thesecond layer is a coating comprising a fluorocarbon material selectedfrom the group consisting of thermoplastics and amorphous fluorocarbons.

The assembly according to the second exemplary aspect, wherein thesecond layer is a coating comprising one or more of the group consistingof a silicone, a wax, a polyethylene, a hot-end, a parylene, and adiamond-like coating preparation.

The assembly according to the second exemplary aspect, wherein thesecond layer is a coating comprising a material selected from the groupconsisting of zinc oxide, molybdenum disulfide, tungsten disulfide,hexagonal boron nitride, and aluminum magnesium boride.

The assembly according to the second exemplary aspect, wherein thesecond layer is a coating comprising an additive selected from the groupconsisting of zinc oxide, molybdenum disulfide, tungsten disulfide,hexagonal boron nitride, and aluminum magnesium boride.

The assembly of any one of the preceding first exemplary aspects,wherein the compressive stress region comprises a maximum flaw size of 5μm or less at the first primary surface of the glass layer.

The assembly of any one of the preceding first exemplary aspects,wherein the compressive stress region comprises a maximum flaw size of2.5 μm or less at the first primary surface of the glass layer.

The assembly of any one of the preceding first exemplary aspects,wherein the compressive stress region comprises a maximum flaw size of0.4 μm or less at the first primary surface of the glass layer.

The assembly of any one of the preceding first exemplary aspects,wherein the glass element is further characterized by an absence offailure when the element is held at a bend radius from about 3 mm toabout 20 mm for at least 120 hours at about 25° C. and about 50%relative humidity.

The assembly of any one of the preceding first and second exemplaryaspects, wherein the glass element and the second layer having a lowcoefficient of friction are configured for use in a display device.

The assembly of any one of the preceding first exemplary aspects,wherein the compressive stress region comprises a plurality ofion-exchangeable metal ions and a plurality of ion-exchanged metal ions,the ion-exchanged metal ions having an atomic radius larger than theatomic radius of the ion-exchangeable metal ions.

The assembly of any one of the preceding first exemplary aspects,wherein the glass layer further comprises an edge, and the glass elementfurther comprises an edge compressive stress region extending from theedge to an edge depth in the glass layer, the edge compressive stressregion defined by a compressive stress of at least about 100 MPa at theedge.

According to a third exemplary aspect, a stack assembly is providedaccording to the first exemplary aspect, wherein the glass layer furthercomprises a core region, and a first and a second clad region disposedon the core region, and further wherein the coefficient of thermalexpansion for the core region is greater than the coefficient of thermalexpansion for the clad regions.

The assembly according to the third exemplary aspect, wherein the coreregion has a core thickness, the first and second clad regions have afirst and a second clad thickness, and a thickness ratio is given by thecore thickness divided by the sum of the first and the second cladthickness, and further wherein the thickness ratio is greater than orequal to three.

The assembly of any one of the preceding first exemplary aspects,wherein the glass element further comprises one or more additional glasslayers disposed beneath the first glass layer.

The assembly of any one of the preceding first exemplary aspects,wherein the glass element further comprises two additional glass layersdisposed beneath the first glass layer.

According to a fourth exemplary aspect, a stack assembly is providedaccording to the first exemplary aspect, further comprising: a glassstructure having a thickness greater than the thickness of the glasselement and two substantially parallel edge surfaces, the structurecomprising the glass element, wherein the element is arranged in acentral region of the structure between the substantially parallel edgesurfaces.

According to a fifth exemplary aspect, a glass article is provided thatcomprises: a glass layer having a thickness from about 25 μm to about125 μm, the layer further comprising: (a) a first primary surface; (b) asecond primary surface; and (c) a compressive stress region extendingfrom the first primary surface of the glass layer to a first depth inthe glass layer, the region defined by a compressive stress of at leastabout 100 MPa at the first primary surface of the layer. The glass layeris characterized by: (a) an absence of failure when the layer is held ata bend radius from about 3 mm to about 20 mm for at least 60 minutes atabout 25° C. and about 50% relative humidity; (b) a puncture resistanceof greater than about 1.5 kgf when the second primary surface of thelayer is supported by (i) an approximately 25 μm thickpressure-sensitive adhesive having an elastic modulus of less than about1 GPa and (ii) an approximately 50 μm thick polyethylene terephthalatelayer having an elastic modulus of less than about 10 GPa, and the firstprimary surface of the layer is loaded with a stainless steel pin havinga flat bottom with a 200 μm diameter; and (c) a pencil hardness ofgreater than 8H.

The assembly of the preceding fifth exemplary aspect, wherein the glasslayer comprises an alkali-free or alkali-containing aluminosilicate,borosilicate, boroaluminosilicate, or silicate glass composition.

The assembly of any one of the preceding fifth exemplary aspects,wherein the thickness of the layer is from about 50 μm to about 100 μm.

The assembly of any one of the fifth second exemplary aspects, whereinthe bend radius of the layer is from about 3 mm to about 10 mm.

The assembly of any one of the preceding fifth exemplary aspects,wherein the compressive stress at the first primary surface of the glasslayer is from about 600 MPa to 1000 MPa.

The assembly of any one of the preceding fifth exemplary aspects,wherein the first depth is set at approximately one third of thethickness of the glass layer or less from the first primary surface ofthe glass layer.

According to a sixth exemplary aspect, a stack assembly is providedaccording to the fifth exemplary aspect, further comprising: a secondlayer having a low coefficient of friction disposed on the first primarysurface of the glass layer.

The assembly of any one of the preceding fifth exemplary aspects,wherein the compressive stress region comprises a maximum flaw size of 5μm or less at the first primary surface of the glass layer.

The assembly of any one of the preceding fifth exemplary aspects,wherein the glass layer is further characterized by an absence offailure when the layer is held at a bend radius from about 3 mm to about20 mm for at least 120 hours at about 25° C. and about 50% relativehumidity.

The assembly of any one of the preceding fifth exemplary aspects and thesixth exemplary aspect, wherein the glass layer and the second layerhaving a low coefficient of friction are configured for use in a displaydevice.

The assembly of any one of the preceding fifth exemplary aspects,wherein the compressive stress region comprises a plurality ofion-exchangeable metal ions and a plurality of ion-exchanged metal ions,the ion-exchanged metal ions having an atomic radius larger than theatomic radius of the ion-exchangeable metal ions.

The assembly of any one of the preceding fifth exemplary aspects,wherein the glass layer further comprises an edge, and an edgecompressive stress region extending from the edge to an edge depth inthe glass layer, the edge compressive stress region defined by acompressive stress of at least about 100 MPa at the edge.

The assembly of any one of the preceding fifth exemplary aspects,wherein the glass layer further comprises a core region, and a first anda second clad region disposed on the core region, and further whereinthe coefficient of thermal expansion for the core region is greater thanthe coefficient of thermal expansion for the clad regions.

The assembly of any one of the preceding fifth exemplary aspects,wherein the core region has a core thickness, the first and second cladregions have a first and a second clad thickness, and a thickness ratiois given by the core thickness divided by the sum of the first and thesecond clad thickness, and further wherein the thickness ratio isgreater than or equal to three.

According to a seventh exemplary aspect, a stack assembly is providedaccording to the fifth exemplary aspect, further comprising: a glassstructure having a thickness greater than the thickness of the glasslayer and two substantially parallel edge surfaces, the structurecomprising the glass layer, wherein the layer is arranged in a centralregion of the structure between the substantially parallel edgesurfaces.

According to an eighth exemplary aspect, a method of making a stackassembly is provided that comprises the steps: forming a first glasslayer having a first primary surface, a compressive stress regionextending from the first primary surface of the glass layer to a firstdepth in the glass layer, and a final thickness, wherein the region isdefined by a compressive stress of at least about 100 MPa at the firstprimary surface of the layer; and forming a glass element having athickness from about 25 μm to about 125 μm, the element furthercomprising the glass layer, a first primary surface, and a secondprimary surface. The glass element is characterized by: (a) an absenceof failure when the element is held at a bend radius from about 3 mm toabout 20 mm for at least 60 minutes at about 25° C. and about 50%relative humidity; (b) a puncture resistance of greater than about 1.5kgf when the second primary surface of the element is supported by (i)an approximately 25 μm thick pressure-sensitive adhesive having anelastic modulus of less than about 1 GPa and (ii) an approximately 50 μmthick polyethylene terephthalate layer having an elastic modulus of lessthan about 10 GPa, and the first primary surface of the element isloaded with a stainless steel pin having a flat bottom with a 200 μmdiameter; and (c) a pencil hardness of greater than 8H.

The method according to the eighth exemplary aspect, wherein the step offorming the first glass layer comprises a forming process selected fromthe group consisting of fusion, slot drawing, rolling, redrawing andfloat processes, the forming process further configured to form theglass layer to the final thickness.

The method according to any of the eighth exemplary aspects, wherein thestep of forming the first glass layer comprises a forming processselected from the group consisting of fusion, slot drawing, rolling,redrawing and float processes, and a material removal process configuredto remove material from the glass layer to reach the final thickness.

The method according to any of the eighth exemplary aspects, wherein theglass layer comprises an alkali-free or alkali-containingaluminosilicate, borosilicate, boroaluminosilicate, or silicate glasscomposition.

According to a ninth exemplary aspect, a method is provided according tothe eighth exemplary aspect, wherein the step of forming a compressivestress region extending from the first primary surface of the glasslayer to a first depth in the glass layer comprises: providing astrengthening bath comprising a plurality of ion-exchanging metal ionshaving an atomic radius larger in size than the atomic radius of aplurality ion-exchangeable metal ions contained in the glass layer; andsubmersing the glass layer in the strengthening bath to exchange aportion of the plurality of ion-exchangeable metal ions in the glasslayer with a portion of the plurality of the ion-exchanging metal ionsin the strengthening bath to form a compressive stress region extendingfrom the first primary surface to the first depth in the glass layer.

The method according to the ninth exemplary aspect, wherein thesubmersing step comprises submersing the glass layer in thestrengthening bath at about 400° C. to about 450° C. for about 15minutes to about 180 minutes.

According to a tenth exemplary aspect, a method is provided according tothe eighth exemplary aspect, further comprising the step: removing about1 μm to about 5 μm from the final thickness of the glass layer at thefirst primary surface after the step of forming the compressive stressregion.

The method according to any of the eighth exemplary aspects, wherein thefinal thickness is from about 50 μm to about 100 μm.

The method according to any of the eighth exemplary aspects, wherein thebend radius is from about 3 mm to about 10 mm.

The method according to any of the eighth exemplary aspects, wherein thecompressive stress is from about 600 MPa to 1000 MPa.

The method according to any of the eighth exemplary aspects, wherein thefirst depth is set at approximately one third of the final thickness ofthe glass layer or less from the first primary surface of the glasslayer.

According to an eleventh exemplary aspect, a method is providedaccording to the eight exemplary aspect, wherein the step of forming thefirst glass layer further comprises: forming a core region; and forminga first and a second clad region disposed on the core region, andfurther wherein the coefficient of thermal expansion for the core regionis greater than the coefficient of thermal expansion for the cladregions.

The method according to the eleventh exemplary aspect, wherein the coreregion has a core thickness, the first and second clad regions have afirst and a second clad thickness, and a thickness ratio is given by thecore thickness divided by the sum of the first and the second cladthickness, and further wherein the thickness ratio is greater than orequal to three.

The method according to any of the eighth exemplary aspects, furthercomprising the step: forming a second layer having a low coefficient offriction disposed on the first primary surface of the glass layer.

The method according to the tenth exemplary aspect, wherein the removingstep is conducted such that the compressive stress region comprises amaximum flaw size of 5 μm or less at the first primary surface of theglass layer.

The method according to the tenth exemplary aspect, wherein the removingstep is conducted such that the compressive stress region comprises amaximum flaw size of 2.5 μm or less at the first primary surface of theglass layer.

The method according to any of the eighth exemplary aspects, wherein theglass layer is further characterized by an absence of failure when thelayer is held at a bend radius from about 3 mm to about 20 mm for atleast 120 hours at about 25° C. and about 50% relative humidity.

According to a twelfth aspect, there is provided a glass substratecomprising: a first thickness providing a puncture resistance of atleast 3 Kg force; and a second thickness providing the substrate theability to achieve a bend radius of 5 mm.

According to a thirteenth aspect, there is provided the glass substrateof aspect 12, wherein the second thickness provides the substrate theability to achieve a bend radius of 2 mm.

According to a fourteenth aspect, there is provided the glass substrateof aspect 12, wherein the second thickness provides the substrate theability to achieve a bend radius of 1 mm.

According to a fifteenth aspect, there is provided the glass substrateof any one of aspects 12-14, wherein the second thickness is ≤30microns.

According to a sixteenth aspect, there is provided the glass substrateof any one of aspects 12-14, wherein the second thickness is ≤25microns.

According to a seventeenth aspect, there is provided the glass substrateof any one of aspects 12-16, further comprising a length, and whereinthe second thickness is continuously provided across the entire length.

According to an eighteenth aspect, there is provided the glass substrateof any one of aspects 12-17, further comprising a protective memberdisposed so as to cover a portion of the substrate having the secondthickness.

According to a nineteenth aspect, there is provided the glass substrateof any one of aspects 12-18, wherein the first thickness is ≥130microns.

According to a twentieth aspect, there is provided the glass substrateof any one of aspects 12-19, wherein the glass substrate comprises acomposition that is an alkali-free, alumino-boro-silicate, glass.

According to a twenty-first aspect, there is provided the glasssubstrate of any one of aspects 12-20, capable of at least 100 cycles ofbending to a 5 mm radius before failure.

According to a twenty-second aspect, there is provided the glasssubstrate of any one of aspects 12-21, further comprising a Young'smodulus of >50 GPa.

According to a twenty-third aspect, there is provided the glasssubstrate of any one of aspects 12-22, having a pencil hardness of atleast 8H.

According to a twenty-fourth aspect, there is provided a display devicecomprising a body and a cover glass, wherein the cover glass comprisesthe glass substrate of any one of aspects 12-23.

According to a twenty-fifth aspect, there is provided a method ofetching glass comprising: obtaining a substrate having a firstthickness, wherein the first thickness provides the substrate with apuncture resistance of at least 3 kgf force; and removing a portion ofthe substrate so as to achieve a second thickness, the second thicknessbeing less than the first, wherein the second thickness provides thesubstrate the ability to achieve a bend radius of 5 mm, wherein afterthe removing, the substrate maintains a portion having the firstthickness.

According to a twenty-sixth aspect, there is provided the method ofaspect 25, wherein the removing is performed by etching.

According to a twenty-seventh aspect, there is provided the method ofaspect 25 or aspect 26, wherein the second thickness provides thesubstrate the ability to achieve a bend radius of 2 mm.

According to a twenty-eighth aspect, there is provided the method ofaspect 25 or 26, wherein the second thickness provides the substrate theability to achieve a bend radius of 1 mm.

According to a twenty-ninth aspect, there is provided the method of anyone of aspects 25-28, wherein the second thickness is ≤30 microns.

According to a thirtieth aspect, there is provided the method of any oneof aspects 25-28, wherein the second thickness is ≤25 microns.

According to a thirty-first aspect, there is provided the method of anyone of aspects 25-30, wherein the substrate comprises a length, andwherein removing provides the second thickness continuously across theentire length.

According to a thirty-second aspect, there is provided the method of anyone of aspects 25-31, further comprising disposing a protective memberto cover a portion of the substrate having the second thickness.

According to a thirty-third aspect, there is provided the method of anyone of aspects 25-32, wherein the first thickness is ≥130 microns.

According to a thirty-fourth aspect, there is provided the method of anyone of aspects 25-33, wherein the glass substrate comprises acomposition that is an alkali-free, alumino-boro-silicate, glass.

According to a thirty-fifth aspect, there is provided the method of anyone of aspects 25-34, wherein the substrate comprises an edge, and themethod further comprising etching the edge.

According to a thirty-sixth aspect, there is provided the method ofaspect 35, wherein etching the edge is performed simultaneously with theremoving.

According to a thirty-seventh aspect, there is provided the method ofany one of aspects 25-36, wherein the glass substrate comprises aYoung's modulus of >50 GPa.

According to a thirty-eighth aspect, there is provided the method ofaspect 25-37, wherein the glass substrate comprises a pencil hardness ofat least 8H.

According to a thirty ninth aspect, there is provided a glass article,comprising:

a glass element having a thickness from about 25 μm to about 125 μm, theglass element further comprising:

(a) a first primary surface;

(b) a second primary surface; and

(c) a compressive stress region extending from the first primary surfaceof the glass element to a first depth in the glass element, the regiondefined by a compressive stress 6I of at least about 100 MPa at thefirst primary surface of the glass element,

wherein the glass element is characterized by:

(a) a stress profile such that when the glass element is bent to atarget bend radius of from 1 mm to 20 mm, with the center of curvatureon the side of the second primary surface so as to induce a bendingstress σB at the first primary surface, σI+σB<0; and

(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.

According to a fortieth aspect, there is provided the glass article ofaspect 39, wherein σI+σB<0 to a depth of at least one micron below thefirst primary surface.

According to a forty first aspect, there is provided the glass articleof aspect 39, wherein σI+σB<0 to a depth of at least two microns belowthe first primary surface.

According to a forty second aspect, there is provided the glass articleof aspect 39, wherein σI+σB<0 to a depth of at least three microns belowthe first primary surface.

According to a forty third aspect, there is provided glass article,comprising:

a glass element having a thickness from about 25 μm to about 125 μm, theglass element further comprising:

(a) a first primary surface;

(b) a second primary surface; and

(c) a compressive stress region extending from the first primary surfaceof the glass element to a first depth in the glass element, the regiondefined by a compressive stress of at least about 100 MPa at the firstprimary surface of the glass element,

wherein the glass element is characterized by:

(a) an absence of failure when the glass element is subject to 200,000cycles of bending to a target bend radius of from 1 mm to 20 mm, by theparallel plate method;

(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.

According to a forty fourth aspect, there is provided glass article,comprising:

a glass element having a thickness from about 25 μm to about 125 μm, theglass element further comprising:

(a) a first primary surface;

(b) a second primary surface; and

(c) a compressive stress region extending from the first primary surfaceof the glass element to a first depth in the glass element, the regiondefined by a compressive stress of at least about 100 MPa at the firstprimary surface of the glass element,

wherein the glass element is characterized by:

(a) an absence of failure when the glass element is held at a bendradius from about 1 mm to about 20 mm for at least 60 minutes at about25° C. and about 50% relative humidity;

(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.

According to a forty fifth aspect, there is provided the article of anyone of aspects 39-44, the glass element comprising (c) a pencil hardnessof greater than or equal to 8H.

According to a forty sixth aspect, there is provided the article of anyone of aspects 39-45, the glass element comprising a plurality oflayers.

According to a forty seventh aspect, there is provided the article ofaspect 46, wherein each of the plurality of layers has the sameconfiguration.

According to a forty eighth aspect, there is provided the article of anyone of aspects 39-47, the glass element comprises a puncture resistanceof greater than about 1.5 kgf when the first primary surface of theglass element is loaded with a stainless steel pin having a flat bottomwith a 200 μm diameter.

According to a forty ninth aspect, there is provided the article of anyone of aspects 39-48, the glass element comprises a puncture resistanceof greater than about 1.5 kgf when the first primary surface of theglass element is loaded with a tungsten carbide ball having a diameterof 1.0 mm.

According to a fiftieth aspect, there is provided the article of any oneof aspects 39-49, the glass element comprises a puncture resistance ofgreater than about 1 kgf when the first primary surface of the glasselement is loaded with a tungsten carbide ball having a diameter of 0.5mm.

According to a fifty first aspect, there is provided the article of anyone of aspects 39-50, wherein when the first primary surface of theglass element is subject to a 1 kgf load from a Vickers indenter, thereis introduced a flaw of ≤100 microns in the first primary surface.

According to a fifty second aspect, there is provided the article of anyone of aspects 39-50, wherein when the first primary surface of theglass element is subject to a 2 kgf load from a Vickers indenter, thereis introduced a flaw of ≤100 microns in the first primary surface.

According to a fifty third aspect, there is provided the article of anyone of aspects 39-52, wherein the glass element has a Vickers hardnessof 550 to 650 kgf/mm2.

According to a fifty fourth aspect, there is provided the article of anyone of aspects 39-53, wherein the glass element has a retained B10 bendstrength of greater than 800 MPa after contact with a cube cornerdiamond indenter loaded with 10 gf.

According to a fifty fifth aspect, there is provided the article of anyone of aspects 39-54, comprising F/w≤0.76 N/mm, wherein F is the closingforce to put the glass element at the target bend radius, and w is thedimension of the glass element in a direction parallel to the axisaround which the glass is bent

According to a fifty sixth aspect, there is provided the article of anyone of aspects 39-55, wherein the glass element comprises an alkali-freeor alkali-containing aluminosilicate, borosilicate, boroaluminosilicate,or silicate glass composition.

According to a fifty seventh aspect, there is provided the article ofany one of aspects 39-56, wherein the thickness of the glass element isfrom about 50 μm to about 100 μm.

According to a fifty eighth aspect, there is provided the article anyone of aspects 39-57, wherein the bend radius of the glass element isfrom about 3 mm to about 10 mm.

According to a fifty ninth aspect, there is provided the article of anyone of aspects 39-58, wherein the compressive stress at the firstprimary surface of the glass element is from about 600 MPa to 1000 MPa.

According to a sixtieth aspect, there is provided the article of any oneof aspects 39-59, wherein the first depth is set at approximately onethird of the thickness of the glass element or less from the firstprimary surface of the glass element.

According to a sixty first aspect, there is provided the article of anyone of aspects 39-60, further comprising:

a second layer having a low coefficient of friction disposed on thefirst primary surface of the glass element.

According to a sixty second aspect, there is provided the article of anyone of aspects 39-61, wherein the compressive stress region comprises amaximum flaw size of 5 μm or less at the first primary surface of theglass element.

According to a sixty third aspect, there is provided the article of anyone of aspects 39-62, wherein the compressive stress region comprises aplurality of ion-exchangeable metal ions and a plurality ofion-exchanged metal ions, the ion-exchanged metal ions having an atomicradius larger than the atomic radius of the ion-exchangeable metal ions.

According to a sixty fourth aspect, there is provided the article of 63,wherein the glass element further comprises an edge, and an edgecompressive stress region extending from the edge to an edge depth inthe glass element, the edge compressive stress region defined by acompressive stress of at least about 100 MPa at the edge.

According to a sixty fifth aspect, there is provided a foldableelectronic device, comprising:

an electronic device having a foldable feature,

wherein the foldable feature comprises the stack assembly according toaspect 39-64.

According to a sixty sixth aspect, there is provided a method of makinga stack assembly, comprising the steps:

forming a glass element having a thickness from about 25 μm to about 125μm, the glass element further comprising:

(a) a first primary surface;

(b) a second primary surface; and

(c) a compressive stress region extending from the first primary surfaceof the glass element to a first depth in the glass element, the regiondefined by a compressive stress 6I of at least about 100 MPa at thefirst primary surface of the glass element,

wherein the glass element is characterized by:

(a) a stress profile such that when the glass element is bent to atarget bend radius of from 1 mm to 20 mm, with the center of curvatureon the side of the second primary surface so as to induce a bendingstress σB at the first primary surface, σI+σB<0; and

(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.

According to a sixty seventh aspect, there is provided the glass articleof aspect 66, wherein σI+σB<0 to a depth of at least one micron belowthe first primary surface.

According to a sixty eighth aspect, there is provided the glass articleof aspect 66, wherein σI+σB<0 to a depth of at least two microns belowthe first primary surface.

According to a sixty ninth aspect, there is provided the glass articleof aspect 66, wherein σI+σB<0 to a depth of at least three microns belowthe first primary surface.

According to a seventieth aspect, there is provided a method of making astack assembly, comprising the steps:

forming a glass element having a thickness from about 25 μm to about 125μm, the glass element further comprising:

(a) a first primary surface;

(b) a second primary surface; and

(c) a compressive stress region extending from the first primary surfaceof the glass element to a first depth in the glass element, the regiondefined by a compressive stress of at least about 100 MPa at the firstprimary surface of the glass element,

wherein the glass element is characterized by:

(a) an absence of failure when the glass element is subject to 200,000cycles of bending to a target bend radius of from 1 mm to 20 mm, by theparallel plate method;

(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.

According to a seventy first aspect, there is provided a method ofmaking a stack assembly, comprising the steps:

forming a first glass element having a first primary surface, acompressive stress region extending from the first primary surface ofthe glass element to a first depth in the glass element, and a finalthickness, wherein the region is defined by a compressive stress of atleast about 100 MPa at the first primary surface of the glass element,

wherein the glass element is characterized by:

(a) an absence of failure when the glass element is held at a bendradius from about 1 mm to about 20 mm for at least 60 minutes at about25° C. and about 50% relative humidity;

(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.

According to a seventy second aspect, there is provided the method ofany one of aspects 66-71, wherein the step of forming the first glasslayer comprises a forming process selected from the group consisting offusion, slot drawing, rolling, redrawing and float processes, theforming process further configured to form the glass layer to the finalthickness.

According to a seventy third aspect, there is provided the method of anyone of aspects 66-71, wherein the step of forming the first glass layercomprises a forming process selected from the group consisting offusion, slot drawing, rolling, redrawing and float processes, and amaterial removal process that removes material from the glass layer toreach the final thickness.

According to a seventy fourth aspect, there is provided the method ofany one of aspects 66-73, wherein the glass layer comprises analkali-free or alkali-containing aluminosilicate, borosilicate,boroaluminosilicate, or silicate glass composition.

According to a seventy fifth aspect, there is provided the method of anyone of aspects 66-74, wherein the step of forming a compressive stressregion extending from the first primary surface of the glass layer to afirst depth in the glass layer comprises:

providing a strengthening bath comprising a plurality of ion-exchangingmetal ions having an atomic radius larger in size than the atomic radiusof a plurality ion-exchangeable metal ions contained in the glass layer;and

submersing the glass layer in the strengthening bath to exchange aportion of the plurality of ion-exchangeable metal ions in the glasslayer with a portion of the plurality of the ion-exchanging metal ionsin the strengthening bath to form a compressive stress region extendingfrom the first primary surface to the first depth in the glass layer.

According to a seventy sixth aspect, there is provided the method ofaspect 75, wherein the submersing step comprises submersing the glasslayer in the strengthening bath at about 400° C. to about 450° C. forabout 15 minutes to about 180 minutes.

According to a seventy seventh aspect, there is provided the method ofany one of aspects 66-76, further comprising the step:

removing about 1 μm to about 5 μm from the final thickness of the glasslayer at the first primary surface after the step of forming thecompressive stress region.

According to a seventy eighth aspect, there is provided the method ofaspect 75 or aspect 76, further comprising the step:

removing about 1 μm to about 5 μm from the final thickness of the glasslayer at the first primary surface after the step of forming thecompressive stress region, wherein the removing step is conducted afterthe submersing the glass layer step.

According to a seventy ninth aspect, there is provided the method of anyone of aspects 66-78, wherein the compressive stress is from about 600MPa to 1000 MPa.

According to a eightieth aspect, there is provided the method of any oneof aspects 66-79, the glass element comprising a pencil hardness ofgreater than or equal to 8H.

According to a eighty first aspect, there is provided the method of anyone of aspects 66-80, the glass element comprising a plurality oflayers.

According to a eighty second aspect, there is provided the method ofaspect 81, wherein each of the plurality of layers has the sameconfiguration.

According to a eighty third aspect, there is provided the method of anyone of aspects 66-82, the glass element comprises a puncture resistanceof greater than about 1.5 kgf when the first primary surface of theglass element is loaded with a stainless steel pin having a flat bottomwith a 200 μm diameter.

According to a eighty fourth aspect, there is provided the method of anyone of aspects 66-83, the glass element comprises a puncture resistanceof greater than about 1.5 kgf when the first primary surface of theglass element is loaded with a tungsten carbide ball having a diameterof 1.0 mm.

According to a eighty fifth aspect, there is provided the method of anyone of aspects 66-84, the glass element comprises a puncture resistanceof greater than about 1 kgf when the first primary surface of the glasselement is loaded with a tungsten carbide ball having a diameter of 0.5mm.

According to a eighty sixth aspect, there is provided the method of anyone of aspects 66-85, wherein when the first primary surface of theglass element is subject to a 1 kgf load from a Vickers indenter, thereis introduced a flaw of ≤100 microns in the first primary surface.

According to a eighty seventh aspect, there is provided the method of85, wherein when the first primary surface of the glass element issubject to a 2 kgf load from a Vickers indenter, there is introduced aflaw of ≤100 microns in the first primary surface.

According to a eighty eighth aspect, there is provided the method of anyone of aspects 66-87, wherein the glass element has a Vickers hardnessof 550 to 650 kgf/mm2.

According to a eighty ninth aspect, there is provided the method of anyone of aspects 66-88, wherein the glass element has a retained B10 bendstrength of greater than 800 MPa after contact with a cube cornerdiamond indenter loaded with 10 gf

According to a ninetieth aspect, there is provided the method of any oneof aspects 66-89, comprising F/w≤0.76 N/mm, wherein F is the closingforce to put the glass element at the target bend radius, and w is thedimension of the glass element in a direction parallel to the axisaround which the glass is bent.

What is claimed is:
 1. A glass article, comprising: a glass elementhaving a thickness from about 25 μm to about 125 μm, the glass elementfurther comprising: (a) a first primary surface; (b) a second primarysurface; and (c) a compressive stress region extending from the firstprimary surface of the glass element to a first depth in the glasselement, the region defined by a compressive stress of at least about150 MPa at the first primary surface of the glass element, (d) a maximumflaw size of less than or equal to 2 microns at the first primarysurface of the glass element; and (e) a stress intensity factor (K) ofless than or equal to 0.2 MPa √m, wherein the glass element ischaracterized by: (a) an absence of failure when the glass element isheld at a bend radius induced by a parallel plate spacing of about 20 mmfor about 60 minutes at about 25° C. and about 50% relative humidity;and (b) a puncture resistance of greater than about 1.5 kgf when thefirst primary surface of the glass element is loaded with a tungstencarbide ball having a diameter of 1.5 mm.
 2. The article of claim 1, theglass element comprising (c) a pencil hardness of greater than or equalto 8H.
 3. The article of claim 2, wherein the compressive stress at thefirst primary surface of the glass element is less than or equal to 2000MPa.
 4. The article of claim 3, wherein the first depth is set atapproximately one third of the thickness of the glass element or lessfrom the first primary surface of the glass element.
 5. The article ofclaim 4, wherein the compressive stress region comprises a plurality ofion-exchangeable metal ions and a plurality of ion-exchanged metal ions,the ion-exchanged metal ions having an atomic radius larger than theatomic radius of the ion-exchangeable metal ions.
 6. The article ofclaim 5, wherein the glass element further comprises an edge, and anedge compressive stress region extending from the edge to an edge depthin the glass element, the edge compressive stress region defined by acompressive stress of at least about 100 MPa at the edge.
 7. The articleof claim 6, wherein the glass element has a Vickers hardness of 550 to650 kgf/mm².
 8. The article of claim 7, wherein the thickness of theglass element is from about 50 μm to about 100 μm.
 9. The article ofclaim 7, wherein the glass element has a retained B10 bend strength ofgreater than 800 MPa after contact with a cube corner diamond indenterloaded with 10 gf.
 10. The article of claim 9, wherein when the firstprimary surface of the glass element is subject to a 1 kgf load from aVickers indenter, there is introduced a flaw of <100 microns in thefirst primary surface.
 11. The article of claim 7, the glass elementcomprising a plurality of layers.
 12. The article of claim 7, comprisingF/w <0.076 N/mm, wherein F is the closing force to put the glass elementat the bend radius, and w is the dimension of the glass element in adirection parallel to the axis around which the glass is bent.
 13. Thearticle of claim 7, further comprising: acoefficient-of-friction-reducing layer disposed on the first primarysurface of the glass element.
 14. A foldable electronic device,comprising: an electronic device having a foldable feature, wherein thefoldable feature comprises the glass element according to claim
 7. 15. Aglass article, comprising: a glass element having a thickness from about50 μm to about 75 μm, the glass element further comprising: (a) a firstprimary surface; (b) a second primary surface; (c) a compressive stressregion extending from the first primary surface of the glass element toa first depth in the glass element, the region defined by a compressivestress of at least about 150 MPa at the first primary surface of theglass element; (d) a maximum flaw size of less than or equal to 400nanometers at the first primary surface of the glass element; and (e) astress intensity factor (K) of less than or equal to 0.3 MPa √m, whereinthe glass element is characterized by: (a) an absence of failure whenthe glass element is held at a bend radius of about 7 mm to about 10 mmfor about 60 minutes at about 25° C. and about 50% relative humidity;(b) a puncture resistance of greater than about 1.5 kgf when the firstprimary surface of the glass element is loaded with a tungsten carbideball having a diameter of 1.5 mm.
 16. The article of claim 15, the glasselement comprising (c) a pencil hardness of greater than or equal to 8H.17. The article of claim 16, wherein the compressive stress at the firstprimary surface of the glass element is less than or equal to 2000 MPa.18. The article of claim 17, wherein the first depth is set atapproximately one third of the thickness of the glass element or lessfrom the first primary surface of the glass element.
 19. The article ofclaim 18, wherein the compressive stress region comprises a plurality ofion-exchangeable metal ions and a plurality of ion-exchanged metal ions,the ion-exchanged metal ions having an atomic radius larger than theatomic radius of the ion-exchangeable metal ions.
 20. The article ofclaim 19, wherein the glass element further comprises an edge, and anedge compressive stress region extending from the edge to an edge depthin the glass element, the edge compressive stress region defined by acompressive stress of at least about 100 MPa at the edge.
 21. Thearticle of claim 20, wherein the glass element has a Vickers hardness of550 to 650 kgf/mm².
 22. The article of claim 21, wherein the glasselement has a retained B10 bend strength of greater than 800 MPa aftercontact with a cube corner diamond indenter loaded with 10 gf.
 23. Thearticle of claim 22, wherein when the first primary surface of the glasselement is subject to a 1 kgf load from a Vickers indenter, there isintroduced a flaw of <100 microns in the first primary surface.
 24. Thearticle of claim 21, the glass element comprising a plurality of layers.25. The article of claim 21, comprising F/w <0.076 N/mm, wherein F isthe closing force to put the glass element at the bend radius, and w isthe dimension of the glass element in a direction parallel to the axisaround which the glass is bent.
 26. The article of claim 21, furthercomprising: a coefficient-of-friction-reducing layer disposed on thefirst primary surface of the glass element.
 27. A foldable electronicdevice, comprising: an electronic device having a foldable feature,wherein the foldable feature comprises the glass element according toclaim
 21. 28. A glass article, comprising: a glass element having athickness from about 50 μm to about 75 μm, the glass element furthercomprising: (a) a first primary surface; (b) a second primary surface;(c) a compressive stress region extending from the first primary surfaceof the glass element to a first depth in the glass element, the regiondefined by a compressive stress of at least about 150 MPa at the firstprimary surface of the glass element; (d) a maximum flaw size of lessthan or equal to 1.5 microns at the first primary surface of the glasselement; and (e) a stress intensity factor (K) of less than or equal to0.4 MPa √m, wherein the glass element is characterized by: (a) anabsence of failure when the glass element is held at a bend radius ofabout 10 mm to about 20 mm for about 60 minutes at about 25° C. andabout 50% relative humidity; (b) a puncture resistance of greater thanabout 1.5 kgf when the first primary surface of the glass element isloaded with a tungsten carbide ball having a diameter of 1.5 mm.